Lignin Research Paper

Means for Producing an Entirely New Generation of Lignin-Based Plastics

EPA Grant Number: R825370C032
Subproject:this is subproject number 032 , established and managed by the Center Director under grant R825370
(EPA does not fund or establish subprojects; EPA awards and manages the overall grant for this center).

Center:EERC - National Center for Clean Industrial and Treatment Technologies (CenCITT)
Center Director: Crittenden, John C.
Title: Means for Producing an Entirely New Generation of Lignin-Based Plastics
Investigators: Sarkanen, Simo
Institution:University of Minnesota , Michigan Technological University
Current Institution:University of Minnesota
EPA Project Officer: Hahn, Intaek
Project Period:    
RFA: Exploratory Environmental Research Centers (1992) RFA Text |  Recipients Lists
Research Category:Center for Clean Industrial and Treatment Technologies (CenCITT) , Targeted Research

Objective:

The goal is to develop the basic technology necessary for establishing a plant where the first biodegradable plastics that are truly lignin-based can be manufactured. The industrial byproduct, lignin, for producing these plastics, will be isolated from kraft black liquor generated by a pulp mill in International Falls, Minnesota.

Approach:

The successful formulation developed at UM for fabricating 85% industrial kraft lignin based plastics involves solvent casting (in aqueous 82% pyrrolidine) of blends with polyvinyl acetate and two plasticizers (diethyleneglycol dibenzoate and indene). Polyvinyl acetate is a commonly used polymer that, for example, provides the basic material in the familiar white glues where it is present in emulsion form. Solvent casting does not represent a suitable method for producing plastics in an industrial context, but a promising alternative approach is provided by spray-drying aqueous (water-based) kraft lignin solutions into which the polyvinyl acetate has been introduced as an emulsion. Thus, two commercially available polyvinyl acetate based emulsion products have been selected for blending with kraft lignin, "Elmer's Glue-All" (Borden) and "Advantage 1" (Franklin International); the latter contains formaldehyde as a crosslinking agent for greater durability.

The present feasibility study will be completed by employing the spray-dried powders in compression- or injection-molding trials dedicated to fabricating components for tensile testing. Here the impact of degree of association and crosslinking between the molecular constituents in the kraft lignin preparation will be explored upon the mechanical properties of the new biodegradable plastics produced.

Rationale:

The conversion of wood chips to pulp for manufacturing paper generates huge quantities of byproduct, lignin, annually in the United States. The kraft process is still the method that is primarily employed for the purpose by the pulping industry. The best estimates indicate that more than 26 million tons of kraft lignin are generated as byproducts of pulping operations every year. As steps have been taken to maximize production, the recovery furnaces, in an ever increasing number of mills, have become overloaded; the result is that all the byproduct lignin can no longer be used in its traditional role as a fuel. Unfortunately, the necessary capital investment usually precludes construction of a new recovery furnace, so that there is little prospect of rectifying the situation in the majority of recovery-loaded mills. Even though untreated black liquor cannot be discharged directly into rivers, an exacerbation of pollution originating from pulp mills is likely to occur. It is difficult to envisage a more compelling way of responding to the problem than by creating biodegradable plastics from the kraft lignin in surplus black liquor.

Intensive efforts devoted to incorporating lignin preparations into useful polymeric materials have been under way for almost twenty years in a number of laboratories. Generally the most encouraging formulations have resulted from chemical modification and covalent linking into polyurethanes, phenol-formaldehyde resins, epoxies, acrylics, etc. In other cases, promising blends, involving the lignin derivatives themselves, have been created. Despite the judicious schemes devised for fractionating and derivatizing the lignin preparations employed, the optimum lignin contents in these polymeric materials have typically fallen in a range of 25 to 40%.

An approach has now been developed at UM for formulating blends containing 85% underivatized industrial kraft lignin that possess Young's moduli around 1 GPa. Nothing like it has ever before been achieved. The strength properties of these new plastics vary monotonically with the degree of intermolecular association between the constituent kraft lignin components. Thus this marks the birth of the first generation of polymeric materials that are truly lignin-based.

Publications and Presentations:

Publications have been submitted on this subproject: View all 10 publications for this subproject | View all 157 publications for this center

Supplemental Keywords:

biodegradable plastic, lignin, pulp, fabrication., RFA, Scientific Discipline, Geographic Area, Sustainable Industry/Business, Midwest, Chemical Engineering, cleaner production/pollution prevention, Sustainable Environment, State, Chemistry, Technology for Sustainable Environment, Civil/Environmental Engineering, Civil Engineering, New/Innovative technologies, Environmental Engineering, Engineering, Minnesota, biodegradable, polbiny acetate, environmentally conscious manufacturing, pulp, lignin, polymers, biodegradable materials, innovative technology, International Falls, Minnesota, plastics, innovative technologies, pollution prevention, polymer design

Main Center Abstract and Reports:

R825370    EERC - National Center for Clean Industrial and Treatment Technologies (CenCITT)

Subprojects under this Center:(EPA does not fund or establish subprojects; EPA awards and manages the overall grant for this center).
R825370C032 Means for Producing an Entirely New Generation of Lignin-Based Plastics
R825370C042 Environmentally Conscious Design for Construction
R825370C046 Clean Process Advisory System (CPAS) Core Activities
R825370C048 Investigation of the Partial Oxidation of Methane to Methanol in a Simulated Countercurrent Moving Bed Reactor
R825370C054 Predictive Tool for Ultrafiltration Performance
R825370C055 Heuristic Reactor Design for Clean Synthesis and Processing - Separative Reactors
R825370C056 Characterization of Selective Solid Acid Catalysts Towards the Rational Design of Catalytic Reactions
R825370C057 Environmentally Conscious Manufacturing: Prediction of Processing Waste Streams for Discrete Products
R825370C064 The Physical Properties Management System (PPMS™): A P2 Engineering Aid to Support Process Design and Analysis
R825370C065 Development and Testing of Pollution Prevention Design Aids for Process Analysis and Decision Making
R825370C066 Design Tools for Chemical Process Safety: Accident Probability
R825370C067 Environmentally Conscious Manufacturing: Design for Disassembly (DFD) in De-Manufacturing of Products
R825370C068 An Economic Comparison of Wet and Dry Machining
R825370C069 In-Line Copper Recovery Technology
R825370C070 Selective Catalytic Hydrogenation of Lactic Acid
R825370C071 Biosynthesis of Polyhydroxyalkanoate Polymers from Industrial Wastewater
R825370C072 Tin Zeolites for Partial Oxidation Catalysis
R825370C073 Development of a High Performance Photocatalytic Reactor System for the Production of Methanol from Methane in the Gas Phase
R825370C074 Recovery of Waste Polymer Generated by Lost Foam Technology in the Metal Casting Industry
R825370C075 Industrial Implementation of the P2 Framework
R825370C076 Establishing Automated Linkages Between Existing P2-Related Software Design Tools
R825370C077 Integrated Applications of the Clean Process Advisory System to P2-Conscious Process Analysis and Improvement
R825370C078 Development of Environmental Indices for Green Chemical Production and Use

First Higher-value Chemical Derived from Lignin to Hit Market in 2021

As lignin supplies rise on the back of growing cellulosic feedstock utilization, commercialization opportunities of up to $242 billion are emerging in 13 select chemicals, says Lux Research.

BOSTON, MA – July 10, 2014 – Lignin, a component of lignocellulosic biomass and a common byproduct stream from cellulosic conversion processes, has a potential market worth of $242 billion across 13 select products alone, but commercialization of these lignin derived chemicals such as BTX (a mixture of benzene, toluene, and xylene) and cyclohexanol lags growing feedstock supplies, according to Lux Research.

Today, the commercial sale of lignin is limited. Even though the pulp and paper industry produces about 50 million metric tons (MT), most is burned for power with only 1 million MT reaching the chemicals market. However, the supply of lignin from other sources is set to grow. Growing production of fuels from lignocellulosic feedstocks alone is projected to process up to 2.9 million MT in 2017, creating huge opportunities for the creation of higher-value chemicals.

“Lignin is capable of producing a variety of straight chain, cyclic and aromatic chemicals, each with market sizes ranging from the tens of millions of dollars up to the hundred-billion-dollar range,” said Julia Allen, Lux Research Analyst and the lead author of the report titled, “Finding Untapped Value: Converting Lignin to Higher Value Chemicals.”

“But creating higher-value chemicals requires technology development to balance feedstock variability, lignin separation effects, depolymerization, and product separation challenges, which still has significant work ahead,” she added.

Lux Research analysts evaluated technologies to convert lignin into higher-value chemicals and leveraged an invention-to-commercialization model to predict the emergence of such chemicals on the market. Among their findings:

  • First lignin-based value added chemical product expected to launch in 2021. A predictive tool designed by Lux Research – based on historical invention-to-commercialization pathways of major materials – found the lignin-to-chemical innovation cycle to lag that of Polylactic acid (PLA) by 18 years. Consequently, the first lignin-derived chemical product may be expected to hit the market in 2021, following a significant patent inflection in 2018-19.
  • Thermal Routes Appear Best for Near-term. There are four major routes under development to convert lignin into smaller chemical constituents – thermal, chemical, metallic catalytic and biological. Of them, thermal depolymerization, such as pyrolysis, is the most mature, though companies focus on fuels not chemicals. Purely chemical routes are limited in scale, while the metallic catalytic processes to higher-value chemicals have unresolved technical challenges despite being the industry leader in terms of scale, and biological routes lag in commercial development.
  • Wide range of commercialization opportunities exist. Ahead of a second patent inflection in 2018-2019 following the first in 2006-2007, opportunities abound for companies and research institutions to develop processes to convert lignin into higher-value chemicals whose markets can be in the billions of dollars. As continued R&D accelerates, early-stage companies such as Annikki, Biome Bioplastics and Vertichem, as well as universities like the Universite de Sherbrooke and Tohoku Universities, are prime targets for collaboration.

The report, titled “Finding Untapped Value: Converting Lignin to Higher Value Chemicals,” is part of the Lux Research Bio-based Materials and Chemicals Intelligence service.

Thursday, July 10, 2014

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