P A S S I O N. CHE.348 Renewable Resources: Chemistry and Technology I

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1 S C I E N C E T E C H N L G Y P A S S I N CHE.348 Renewable Resources: Chemistry and Technology I Biorefinery / Green Chemistry Processes General, economical and logistical aspects (with a focus on wood based biorefinery processes) Wolfgang Bauer Institute of Paper, Pulp and Fibre Technology (IPZ) Graz University of Technology Austria Contents Background Biorefinery / Green Chemistry (Wood) Biorefineries History / Current / Future Challenges and pportunities (Economy / Logistics) 2 1

2 Contents Background Biorefinery/Green Chemistry (Wood based) Biorefineries History / Current / Future Challenges and pportunities 3 Driving forces Climate change / reduction of GHG emissions Depletion of fossil resources Sustainability Government policies Biobased Economy 4 2

3 Definitions Biobased Economy Within a future sustainable society, biomass is expected to become one of the major renewable resources for the production of food, materials, chemicals, fuels, power and heat. Biological, chemical and chemical engineering sciences have a leading role in the construction of these future industries The term was first defined by Juan Enrique and Rodrigo Martinez in the 1997 AAAS meeting. An excerpt of this paper was published in Science 281 (14 August 1998): Definitions Biorefineries Biorefining concerns the sustainable processing of biomass into a spectrum of marketable products and energy. (EU) Facility that integrates biomass conversion processes and equipment to produce fuels, power and chemicals from biomass (NREL National Renewable Energy Laboratory) EU s vision* is that by 2030, products like biofuels, textiles, chemicals etc. will evolve from established biorefinery operations. To achieve this goal, integrated and flexible biorefineries are required which operate more sustainably than current 6 operations, that are based on fossil resources * EU, Star-Colibri - Strategic Targets for

4 Definitions Green Chemistry Science that aims to reduce or eliminate the use and/or generation of hazardous substances in the design phase of materials development. It requires an inventive and interdisciplinary view of material and product design. Green Chemistry follows the principle that it is better to consider waste prevention options than to dispose or treat waste. It is a process rather than product oriented approach Principles of Green Chemistry 8 4

5 12 Principles of Green Chemistry Evan S. Beach, Zheng Cui, Paul T. Anastas. Energy Environ Sci., 2009, 2, What does green in Green Chemistry really mean? Following the 12 Principles of Green Chemistry When it comes to doing green chemistry properly, using green starting materials is just one point, among several others The green in Green Chemistry must always refer to the whole reaction system, not just to the starting materials. Atom economy Renewabl e feedstocks Catalysts Energy efficiency Green Chemistry Minimum chemical waste Direct syntheses Benign solvents & reagents This includes e.g. reagents, solvents, auxiliaries, experimental setup, purification and work-up, as well as energy aspects (heating, cooling). 5

6 Example: a special chemical for pharmacy Green way from cellulose (waste) 1 reaction step yield 82% solvents: water and ethanol microwave heating, no cooling Catalyst: alumina 92% of involved atoms in product one purification step at the end total time: 3 hours R H H H H Classical way (Synthesis) from glucose / furfural derivatives 13 reaction steps yield 8% six different (chlorinated) solvents heating (+120 C, heating mantle) and cooling (-78 C) involved extensive purification and work-up (after 8 of 13 steps) 24% of involved atoms in product total time: 3-4 days Trisubstituted furan Highly functionalized, low-molecular compound Multiple ways of further reactions and modifications Starting material for the pharmaceutical industry: tuberculostatics, antibiotics, cancerostatics Starting material for the chemical industry: flavoring agents, paints, binders, plastics, special glues 12 Principles of Green Engineering 1. Inherent rather than circumstantial 2. Prevention rather than treatment 3. Design for separation 4. Maximize mass, energy, space, and time efficiency 5. utput-pulled versus input-pushed 6. Conserve complexity 7. Durability rather than immortality 8. Meet need, minimize excess 9. Minimize material diversity 10. Integrate local material and energy flows 11. Design for commercial afterlife 12. Renewable rather than depleting Anastas, P.T., and Zimmerman, J.B., "Design through the Twelve Principles of Green Engineering", Env. Sci. and Tech., 37, 5, 94A-101A,

7 Principle 1 Inherent rather than circumstantial Designers should evaluate the inherent nature of the selected material and energy inputs to ensure that they are as benign as possible as a first step toward a sustainable product, process, or system Principle 2 Prevention rather than treatment It is better to prevent waste than to treat or clean up waste after it is formed Tremendous spent on waste treatment, disposal and remediation; in the past not always considered in cost of plant - full cost accounting (Life Cycle Analysis) Usually requires extra unit operations Industrial mindset is changing 7

8 Principle 3 Design for Separation Many traditional methods for separation require large amounts of hazardous solvents, whereas others consume large quantities of energy as heat or pressure. Appropriate upfront designs permit the selfseparation of products using intrinsic physical/chemical properties. Maximize efficiency Principle 4 Products, processes, and systems should be designed to maximize mass, energy, space and time efficiency Mass and energy efficiency is standard Chemical Engineering optimization Related to Prinicple 8 (no overcapacity) Related to Principle 10 (mass & energy integration) 8

9 Principle 5 uput-pulled rather than input-pushed Approaching design through Le Chatelier s Principle (Any change in status quo prompts an opposing reaction in the responding system), therefore, minimizes the amount of resources consumed to transform inputs into desired outputs Conserve complexity Principle 6 Embedded entropy and complexity must be viewed as an investment when making design choices on recycle, reuse, or beneficial disposition More focused on products than processes Less complicated products can more easily be recycled If a product is complex then it should be designed to be reused 9

10 Principle 7 Durability rather than immortality; It is therefore necessary to design products with a targeted lifetime to avoid immortality of undesirable materials in the environment. However, this strategy must be balanced with the design of products that are durable enough to withstand anticipated operating conditions.. Principle 8 Meet Need, Minimize Excess Design for unnecessary capacity or capability (e.g., one size fits all ) solutions should be considered a design flaw Don t overdesign things Extra size means wasted material and energy 10

11 Principle 9 Minimize material diversity ptions for final disposition are increased through upfront designs that minimize material diversity yet accomplish the needed functions Principle 10 Integrate Material and Energy Flows Design of products, processes, and systems must include integration and interconnectivity with available energy and materials flows Make use of what you ve got available Heat integration (principle 4) Mass integration (principle 4) Industrial parks In process or on site 11

12 Principle 11 Design for commercial afterlife To reduce waste, components that remain functional and valuable can be recovered for reuse and/or reconfiguration. Principle 12 Renewable rather than depleting Material and energy inputs should be renewable rather than depleting Don t deplete our natural resources (renewable materials) Resources to be kept for future generations Energy: solar, wind, hydroelectric, geothermal, biomass, hydrogen (fuel cells) 12

13 How green can/will CHEMISTRY get? CHEMISTRY NATURE GREEN CHEMISTRY? Chemistry Refinery Green Chemistry Biorefinery Products from bio refineries 1) Bio polymers (Bio materials) 2) Bio chemicals 3) Bio fuel 4) Bio energy Definition: refinery / biorefinery Fractionation (separation and purification) of fossil resources / biomass into its main components that are used further to produce an optimum of balanced products 13

14 Looking into the (far) future The basis of the chemical industries, present and future Renewable resources Biorefineries Chemical Industries Fossil resources Petrochemistry In (far) future, fossil resources WILL be used up. If mankind is not to fall back into a rudimental, pre industrial state, the whole production and all flows of the chemical industries will have to be changed from a petrochemical basis to a renewable basis. This requires long term efforts and fundamental research. The economy of the 21 st century must reorient itself Raw materials sources Maribor

15 Either r Contents Background Biorefinery/Green Chemistry (Wood) Biorefineries History / Current / Future Challenges and pportunities 30 15

16 (Wood) Biorefineries - History 31 Wood Biorefineries - History 32 16

17 Wood Biorefineries - History 33 Wood Biorefineries - History 34 17

18 Wood Biorefineries - History 35 Wood Biorefineries - History 36 18

19 Pulp Mills Current status Green Chemistry??? Biorefinery??? 37 RISE (Research Institutes of Sweden), 2015 Renewable Biomass ~ 180 billion tons/year (wood is ~1% of this value) 38 19

20 Green starting materials today Mass balance current situation Plants for biodiesel Plants for biogas Starch for bioethanol Starch for food/feed il plants Sugar 29% Medical plants Fiber plants thers 11.2% 5.8% Wood (pulp, paper, textile, derivatives) thers 91% 44.6% 5.36% 0.446% 1.34% 0.893% 1.34% 9% Wood is - and will remain - the most important renewable starting material for future chemical industries ( biorefineries ). 25% LIGNIN 29% HEMI- CELLULSE CELLULSE 1% 5% 40% Anaximenes (ca. 550 v. Chr.): there are many things made from one single element [fire water earth - air], others from two or three, only wood needs all four of them.. Cellulose ( 1 D ) Me Me DPM Me H ' Me -1 Me --4 H ther natural starting materials: Extractives(fats, oils, isoprenoids) Proteins Starch ther carbohydrates Lignin ( 3 D ) H 4--5 Me 5-5 H Me R H Hemicelluloses ( 2 D ) R H H H H H H H H H Me H Source: Rosenau, Sixta, Bauer, PaPSaTCH PhD Course Advances in Biorefineries, Graz,

21 Pulp mills Current status Pulp and paper industry is in an ideal position to convert to a true biorefinering/green chemistry industry Wood sourcing and logistics Established, added value creating products Good engineering and production base High potential to integrate additional added value products 41 Pulp mills Future A Cellulose 42 21

22 Pulp mills Future A Cellulose CNF/CNC Unique properties: Dimensions: Mechanical (similar to Kevlar) Diameter: ~3 100 nm ptical / electronical Length: ~100nm 100µm Surface / functionalization Quelle:Zimmermannet al. Adv. Eng. Mater (2004) Pulp mills Future A Cellulose Cellulose aerogels: Selected properties cellulose aerogel silica aerogel density [mg cm - ³] > > specific surface [m² g -1 ] (lin) [1/K 10-6 ] at RT sound propagation [km s -1 ] Ultra-leightweight cellulosic bodies for heat, sound and impact insulation and for medicine (cell scaffolds, bone replacement). 22

23 Pulp mills Future B Lignin 45 Carbon Fibres Pulp mills Future B Lignin Plasticizer to enable the shaping of other materials Phenol replacement in MDF/HDF production Phenolic antioxidant, e.g to rubber in tires Black liquor gasification/lignoboost?????? 23

24 Pulp mills Future C Chemical Intermediates 47 Contents Background Biorefinery/Green Chemistry (Wood) Biorefineries History / Current / Future Challenges and pportunities 48 24

25 Challenges What is the future of biorefineries? Renewable resources Biorefineries Fossil resources Petrochemistry 49 Elemental Composition of Feedstock 50 25

26 Development time Time to grow: refinery: 120+ years, biorefinery: just starting Renewable resources Biorefineries Fossil resources Petrochemistry Development time Renewable resources Biorefineries Fossil resources Petrochemistry (Energy and chemicals) Time Today 26

27 -1-4-link Food vs. energy / chemicals -1-6-bridge STARCH -1-4-link H H H H H (Hemi)CELLULSES n the long run, energy and chemicals / materials will be derived from natural resources that have no competitive utilization in the food / feed market. This requires long term research efforts (and might require improved ethical thinking as well). The bio resource service challenge Type of service Service Possible other resources Social Nutrition None Jobs and development for rural regions None Social stability for rural regions None Economic Stability for energy distribution grids Smart grids, hydro power, pumped hydro power, hydrogen, compressed air energy storage, (fossil resources) Transport fuel High temperature industrial heat Electricity (using battery storage), hydrogen, synthetic fuels, (fossil resources) (fossil fuels), H 2 from excess electricity Feedstock for synthetic materials and plastics (fossil resources), sequestered C 2 plus H 2 from excess electricity Feedstock for conventional bio-based None products Environmental Reduction of greenhouse gas emissions Wind and hydro power, solar thermal systems, photovoltaic, oceanic power, geothermal energy Preserving soil fertility None Preserving water and nutrient cycles None Preserving bio-diversity None 27

28 Energetic vs. chemical utilization We need CARBN to produce materials and chemicals. We don t necessarily need CARBN for energy production (there are other and better alternatives)! Renewable resources Biorefineries Fossil resources Petrochemistry Energetic vs. chemical utilization Where do we stand, where shall we go? Renewable resources Biorefineries Fossil resources Petrochemistry Bioethanol Biodiesel (FAME) Biofuels Pyrolysis oils PLA etc. Insulation Fine chemicals From renewables today: 0.8% of plastics 0.4% of insulation 0.06% of platform chemicals The research expenditure for chemical use of renewable resources has increased to 28% compared to energetic uses. EU report, FP7, bioprogress report Taking the final use of the primary products from renewables as a measure, i.e. burning vs. further conversion, 95.4% of EU research funds have supported energetic utilization. McKinsey & Co. Industrial biotech report, Feb

29 Energetic vs. chemical utilization Where do we stand, where shall we go? Renewable resources Biorefineries Chemical and materials from renewables Fossil resources Petrochemistry Energy from renewables Time Today Large parts of today s chemical utilization of renewables is energetic utilization in disguise. This applies equally to research endeavors and research funding. Energetic vs. chemical utilization Where do we stand, where shall we go? 29

30 Holzbilanz EU (Bio) Refinery Gas il Coal Drop in strategy vs. Use as is strategy Acknowledging nature s synthesis efforts Chemical industries Platform Fine chemicals chemicals (commodities) (specialties) Synth. polymers, fibers, paints, pharmaceutics Value created Future C, Hrenewable 2, CH 4, C 2 Hchemistry 5 H ( biorefineries ): (Syn gas, biofuels, pyrolysis) Providing Multiple bond necessary cleavage chemicals (what Breakdown the fossil to fuels C 1 /C 2 -units do today) PLUS Biogas Simplybyfeeding cascade the utilization old PLUS chemical industries Providing special and novel materials by better use of the intrinsic properties If possible: preserving the unique properties of the raw material not just destroying it! Acknowledge and utilize the synthesis and optimization effort of nature! 30

31 Drop in strategy Drop in strategy vs. Use as is strategy Use as is strategy: Use unique functionality of molecule New product 31

32 Example: Poly(lactic acid) (PLA) biomass pretreatment Made from renewable resources Biologically degradable Detour : polymer monomer polymer sugar fermentation lactic acid destillation polymerisation lactide Polylactic acid (PLA) Cascade utilization 1) Chemical utilization 2) Energy utilization Value created Extractives Polymers Biotechnology (fermentation) Chemistry (reactions) Burning Do something with it first! If nothing works you can still burn it! (George A. lah, Nobel Prize Chemisty 1994) Energy usage modes (biogas, pyrolysis oils, direct burning) should be operated only after value-added chemical utilization. A major hindrance in cascade utilization is the insufficient advancement of separation technology and analytical capability today. 32

33 Real-life biorefinery products Starting materials for the chemical industries of the future Natural products Extremely complex mixtures Changing composition Hard to process (consistency) Unknown individual components Unknown mixture composition Unstable upon storage Difficult Logistics The lignin problem Example: Utilization of spruce wood in Norway Bleaching Ethanol plant Thanks to: Borregaard, Norway The amounts of cellulose and lignin produced are roughly the same. Utilization of the bulk lignin has been the bottleneck in all recent biorefinery approaches (irregularity and recalcitrance of lignin). 33

34 Valorization Valorization 34

35 Valorization How green will chemistry get? What s the answer?!? With regard to: Utilization of renewable resources as starting materials Transition: fossil renewable Dictated by scientific facts easy to answer. With regard to: Application of green chemistry principles Green processes, solvents, syntheses, energy inputs Societal and personal responsibilities difficult to answer. 100 %??? 35

36 How green will chemistry get? General future developments Material / chemical utilization Energetic utilization Food / feed if possible Energy / chemicals from food /feedstock Cascade utilization Direct (one step) utilization Better use of nature s ingenuity in synthesis and material production Extensive breakdown of renewables green to oil C, H 2, CH 4, C 2 H 5 H Logistics Resources with long legs Fossil resources High value renewable resources Liquid energy carriers Gas (Methane) Electricity Base chemicals and with short legs Low grade bio-resources (Grass, )! Biogenic by-products (straw, ) Waste (manure. ) Heat 36

37 Resources shape the economic topography Resources with long legs are in global competition Resource with short legs provide major potential for development in the 21 st century These resources might put the economic topography on its head!! Some truths about new resources......solar energy and biogenic resources have some common problems...transport density...time dependent availability...de-centrality 37

38 The Logistical Trap Conversion Material Humidity [%w/w] Energy content [MJ/kg] Density [kg/m³] Energy density [MJ/m³] Incineration Straw (grey) Wheat Rape seed Wood chips Wood pellets Biogas production Grass silage Manure Diesel oil Transport and renewable resources Taking transport density into account kj/mj km 0,9 0,8 0,7 0,6 0,5 0,4 0,3 0,2 0, Energy density MJ/m³ Wood chips straw Corn, wood pellets diesel oil truck rail 1 rail 2 ship 1 ship 2 tractor 38

39 Taking transport density into account 5,7 km transport of manure and 12 km transport of straw with tractor or 40 km transport of wood chips with lorry or 475 km transport of pellets with train or km transport of crude oil with ship or pipeline consume 1 % of the transported energy Raw material provision must come closer! Renewable resources and area Plant size Upper and lower land requirement in km² Transport distance in km with land use 100% 30 % 10 % Logistical consideration Very small 50 t/a Small t/a Medium t/a Industrial t/a Tractor transport, low transport energy Tractor transport, farm site or small community based plant Tractor transport possible for high transport density, regional plant 1, Tractor transport only for high transport density and large land cover fraction, otherwise truck (or rail) transport, large regional or central plant Upper land requirement calculated with 4 t/ha.a (e.g. wood chips), lower limit with 15 t/ha.a (e.g. corn or miscanthus) 39

40 Re thinking size for renewable resource technologies: Bio ethanol case study ption 1: Ethanol production in combination with a biogas combined heat and power (CHP) plant ption 2: Ethanol production in combination with biogas production ption 3: Ethanol production combined with straw combustion Reference: t/a ethanol from corn, conventional energy provision (natural gas) Re thinking size: ecological impact The transport slopes 100 ecological footprint (SPI) m²a/l t/a The fossil pathway option 1 option 2 option t/a 40

41 Re thinking size: economy 1,1 1 0,9 /lt ethanol 0,8 0,7 ptimal Size option 1 option 2 option 3 0,6 0,5 0, ethanol t/a What does that mean in area? Yield: 10 t/ha 1 t corn 0,5 t ethanol t/a ethanol t/a corn t/a ha 20 % corn ha 300 km² radius ~10 km Tractor transport possible! 41

42 Thank you for your attention! 42