By-products from pulping of wood and non-wood raw materials

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1 By-products from pulping of wood and non-wood raw materials Important source of biomass chemicals FIBRA seminar, March 23 rd, 2015 Klaus Niemelä VTT Technical Research Centre of Finland

2 2 Examples of early (chemical) wood industries Naval strores production (turpentine, resin) Thermal processes Tar production & by-products Wood distillation industry (methanol, acetic acid etc) Charcoal manufacture (important e.g. in Sweden for steel industry in the 19 th century impacts on pulping byproducts) Oxalic acid manufacture by alkali fusion of sawdust in the past

3 3 (Hard)wood distillation industry The first industrial large-scale wood biorefinery process Main operation period c s/1930s New plants constructed still in the 1950s/1960s, even later The only industrial source for methanol and acetone until 1910s/1920s Main source for acetic acid Many other products also isolated

4 4 Pulp mill biorefineries: pulp, chemicals, biofuels Chips Pulping process Pulp, paper Process streams Integrated power/energy production Energy Harvesting residues Agromaterials Recovered paper Process(es) Biofuels Chemicals

5 5 Current share of pulping methods (for Mt pulp) No organosolv processes industrially operating Number of pulp mills 40 very many (10 prehydrolysis mills)

6 6 Alkaline (kraft and soda) pulping: Composition of material dissolved into spent liquors (>130 million tons annually) Distribution of black liquor organics Softwood Hardwood 7

7 7 Industrial by-products from alkaline pulping processes (kraft and soda) Currently Turpentine (chemicals, parfymes, vitamins, polymers ) Tall (pine) oil for fatty acids, resin acids, phytosterols Lignin In the past (only) Methanol, ammonia Heat treatment products (acetone, 2-butanone, oils ) Dimethyl sulphide, dimethyl sulphoxide, dimethyl sulphone From the prehydrolysis/extraction-kraft processes (past) Xylose, furfural, hexoses, ethanol, yeasts Polysaccharides

8 8 Current turpentine production (thousand tons)

9 9 Turpentine composition

10 10 Methanol Found in pyroligneous acid (wood distillation) in 1812 Produced in the late 1800s and early 1900s only by dry distillation of (hard)wood Discovered from kraft pulping streams 1908 In 1912, 5 Swedish mills recovered methanol! The production peak in Sweden was in the 1930s (500 t/a) Isolated at 3 Finnish mills in No information found on production outside Scandinavia Nowadays crude methanol produced from foul condensate stripper off-gases (mainly for combustion)

11 11 First mill-scale purification system recently started at Al-Pac, Canada, based on 2-step distillation

12 12

13 13 Ammonia as a by-product Isolation integrated into the separation of turpentine and methanol The method was developed by Alfons Hellström ( ) Applied only at Kotka mill, Finland (in the 1910s) The production peak was in 1917, 8 tons of ammonium sulfate

14 14 Erik Ludvig Rinman Pulp mill biorefinery pioneer (started in Sweden), whose efforts accelerated a lot of studies that still go on

15 15 Heat treatment of black liquor, discovered by Rinman to increase the formation of useful volatile compounds (kg/t pulp) Promising early yields were approximately: Methanol Acetone 2-Butanone Light oils Heavy oils 30 kg 20 kg 20 kg 18 kg 50 kg Industrial-scale process Rinman method operated at a German pine soda pulp mill Was not economically a big success, for technical reasons and for discovery of methanol synthesis.

16 16 Production at Regensburg, Methanol Acetone 2-Butanone Light oil Heavy oil 110 t 49 t 47 t 56 t 198 t

17 17 The Rinman process had a huge impact on studies on pulping spent liquor utilisation Acids Phenols Ketones, etc Heat treatments Oxidations Gasifications, etc Still going strong for the same products

18 18 DMSO Dimethyl sulphoxide (via DMS) More valuable product from black liquor processing Pilot-scale production in Finland from black liquor in the 1940s Knowledge transferred to the USA, wher production from the 1960s to During the recent years, c. 1/3 of global DMSO was from black liquor Also produced in the Soviet Union ( s)

19 19 Tall oil (pine oil) Isolated at numerous softwood kraft pulp mills worldwide Distilled at >20 distilleries to different fatty and resin acid fractions (and residues) Phytosterols also isolated in many countries Production figure steady: 1,4-1,5 million tonnes The main fractions are valuable products Recent interest also for the manufacture of biodiesel Softwood (tall oil and gum rosin) are the only sources of pine rosin

20 20 Alternative source for resin acids: gum rosin

21 21 Rosin use in Europe

22 22 Tall oil fatty acid use in Europe

23 23 Tall oil (TO) phytosterol manufacturers

24 24 Kraft (sulphate) lignins Annual "production" over 60 million tons. Used as a chemical/material: under 150,000 tons. Dominating company: MeadWestwaco, USA New and planned isolation capacity in the US, Canada, Finland

25 25 Kraft lignin (potential) uses Phenolic resins Panelboard adhesives Thermoset resins for moulded products Friction materials Adsorbent materials Foundry resins Insulation materials Decorative laminates Rubber processing Antioxidant applications Printed circuit board resins Animal health applications Composites and biocomposites Carbon fibres (for vehicles and other uses) Synthetic lignosulphonates, with a large number of well-established uses

26 26 Lignin recovery for non-wood soda pulping

27 27

28 28

29 29 Pre-extraction/hydrolysis before pulping Aim to recover a substantial part of hemicelluloses (xylan, glucomannan) as polymers or monomers Pulp properties should not be affected A lot of interest in Europe and North America Sugars to be fermented to ethanol, or succinic acid (150,000 tons of ethanol expected in 400,000-ton softwood pulp mill), or other chemicals Method applied in the 1970s to isolate arabinogalactan before pulping of larch wood chips (St. Regis company, products known as Stractan)

30 30 Prehydrolysis-kraft pulping for the prouction of dissolving pulp From the prehydrolysate, isolated or produced at several mills in the 1960s-1990s (water prehydrolysis) Furfural Xylose Ethanol Fodder yeast (e.g. 20,000 t/a at Bratsk, USSR) Today water vapor hydrolysis used

31 31 Bratsk prehydrolysis plants in the 1970s (USSR)

32 32 Dissolved products from acidic sulphite pulping

33 33 Lignosulphonates - production Annual "production" over 4-5 million tons. Used as a chemical/material: 1.8 million tons. Production in Europe, Asia, North and South America, Africa. Several companies operating, LignoTech dominating.

34 34 Lignosulphonate functionality & substitutes Source: Borregaard

35 35 Vanillin from lignosulphonates Today, 15% of global vanillin production is based on oxidation of lignosulphonates Two producers: Borregaard (Norway), Bailu Papers (China) In the past, also produced in the US, Canada, Japan, USSR, Poland. Many plants closed Isolated by-products include dehydrodivanillin, acetovanillone, and calcum oxalate

36 36 Carbohydrate-based products from sulphite spent liquors Xylose, arabinose Galactose, mannose, rhamnose Fermentation products ethanol, torula yeast, pekilo protein, ribonucleic acids Some fermentations also use aldonic and uronic acids, and acetic acid Furfural Acetic acid The isolation of lignosulphonates and carbohydrate products offer interesting full biorefinery concepts

37 37 Isolation of acetic acid at Lenzing, Austria Food-grade product Furfural isolated at the same time

38 38 Ethanol from wood (sulphite pulping) From: G. Rødsrud (2011)

39 39 Ethanol from wood (sulphite pulping) From: G. Rødsrud (2011)

40 40 Past sulphite ethanol plants in Finland

41 41 Current ethanol producers From: G. Rødsrud (2011)

42 42 Case from Finland, 1980s

43 43 Lenzing biorefinery, Austria Dissolving pulp Pulp mill 50% 39% Furfural 11% Acetic acid Xylose Beech wood Spent liquor The net calorific value corresponds to abt. 220 kg fuel oil per t of pulp produced! Excess energy Source: H. Harms, FTP Conf. 2005

44 44 Borregaard, Norway

45 45 Torula yeast and pekilo protein Pekilo protein produced only at two plants in Finland (1970s-1980s) Torula yeast currently produced at a few countries

46 46 Ribonucleic acids by Nippon Paper

47 47 Semichemical pulp mills High-yield pulp mills (hardwood) for corrugated board, NSSC process originally developed in the US in the 1920s to pulp wood from tannin extraction Pioneering acetic and formic acid separation processes developed in the USA and Finland Savon Sellu Sonoco s Extraction columns for acetic acid

48 48 Chestnut extraction-pulping process operated in Italy Chips Hot water extraction NSSC pulping Pulp Tannin

49 49 Mechanical pulping processes Due to the high pulp yield (85-98%), limited opportunities for byproducts exist Sulfur-free TMP turpentine isolated at a few mills (US, Canada, Sweden, Finland ) Opportunities to isolate and utilise of galactoglucomannan from CTMP process waters thoroughly studied (not in mill-scale)

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