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FuBio – Production of hydroxy acids and products thereof. Workshop 10.12.2010 Groupwork: Recovery from kraft pulp mill process Group leader Raimo Alén, JYU. Recovery from kraft pulp mill process (results of the workshop Dec 10th, 2010). Feedstocks (both softwood and hardwood delignification)
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FuBio – Production of hydroxy acids and products thereof Workshop 10.12.2010 Groupwork: Recovery from kraft pulp mill process Group leader Raimo Alén, JYU
Recovery from kraft pulp mill process (results of the workshop Dec 10th, 2010) Feedstocks (both softwood and hardwood delignification) Black liquor (BL) Effluent from alkaline pretreatment (EAP) chips alkaline preatreatment cooking Effluent from oxygen delignification Hydrolysate from hot-water pretreatment of chips prior to cooking
Recovery from kraft pulp mill process (results of the workshop Dec 10th, 2010) Unit operations The "first" group carbonation (lignin precipitation) Carb electrodialysis (recovery of natrium, acid) ED ion exclusion chromatography (separation of individual acids) IEC distillation (separation of individual acids) D ultrafiltration (separation of lignin) The "second group" extraction (novel solution) adsorption (acids and lignin) esterification plus distillation use of ion exchanges crystallisation (only for pure fractions, not for BL) Define the benefits and disadvantages of main unit operations
Recovery from kraft pulp mill process (results of the workshop Dec 10th, 2010) Some process alternatives separation/recovery process integration to the current process with minimal changes important issues when considering process alternatives material balance sodium recovery the effect of separation method to fibres how much each component will be produced? the effect on BL thermal value the effect on production efficiency (in case recovery boiler is a bottleneck) possibility to produce acetic and formic acid There are a great number of possible process modifications and alternatives!
Recovery from kraft pulp mill process (results of the workshop Dec 10th, 2010) Principles for the process outline Fibre is the main product Efficient recovery of cooking chemicals and extractives Sulfur-free novel by-products Suitable balance between the carbohydrate and lignin degradation products Straightforward separation techniques Versatile modification possibilities
Recovery from kraft pulp mill process (results of the workshop Dec 10th, 2010) i) Simplest solution BL BL UF not an option, H2S! CO2 Carb Lignin NaHCO3/Na2CO3 ED NaOH Free acids - acids as Na-salts - part of lignin left (<15 % of original amount) - inorganic compounds Distillation IEC UF XAD ED +H2SO4 BL residue Na-salts distillation distillation Distillation etc. UF IEC IEC Behaviour of extractives, lignin, sulfur containing inorganics?
Recovery from kraft pulp mill process (results of the workshop Dec 10th, 2010) Pretreatment NaOH Pulping - kraft -soda-AQ Wood Turpentine Crude tall oil Evaporation Fuel gas CO2 Lignin (~75 % of total) Carbonation Evaporation NaHCO3 / Na2CO3 Lignin (~15 % of total) H2SO4 Acidification Evaporation Volatile acids Na2SO4 Crude hydroxy acid fraction Basic process Variable part
Recovery from kraft pulp mill process (results of the workshop Dec 10th, 2010) EAP (effluent from alkaline pretreatment) the same way as BL positive: no sulfur the effect on pulp (fibre) quality? Na-recovery (material balance) OED (effluent from oxygen delignification) same way as EAP PHWT-hydrolysis
Recovery from kraft pulp mill process (results of the workshop Dec 10th, 2010) Patent and other IPR –questions patent and literature review is done by VTT (Black liquor ja hydroksihapot, June 2010) Other potential companies? Hycail (Turku) – polymerisation of hydroxy acids Rinheat Oy (Otaniemi), process calculations, also ED