Commentary - businesschemistry.org · Biodiesel → Intermediate ... It is worth noting that there...
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Introduction A recent report (C&News, 2009) estimates over $100 billion of the current global chemicals mar- ket, about 3%, are derived from either bio-based feedstock or fermentation or enzymatic conver- sion or combination of them. This report projected that the share of bio-derived chemicals would grow to about 15% of global chemical sales by 2025. There are several drivers for the interest and growth of bio products in the marketplace. A few that are worth mentioning include the availabi- lity of cost effective technologies including novel functional building blocks and improved proces- ses, concerns about long term sustainability and price volatility of fossil-based feedstock, a more benign footprint on the environment, and con- sumer interest in green products and public poli- cy. Many large and established chemical and bio- technology companies as well as numerous smal- ler startup and venture companies are actively involved in the development and commerciali- zation of bioproducts from a variety of renewa- ble biomass sources. These companies are trying to follow a bio-refinery model, similar to current petrochemical refineries, which co-produce large volume commodity fuels and high value chemi- cals. This paper covers the following topics related to these emerging technologies: Various bio refinery models Conversion technologies First wave of bioproducts by thermo .. .chemical/catalytic conversion of bio- .. .derived feedstock Bio feedstock platforms Second wave of bioproducts by bioche Commentary Bio products from bio refineries - trends, challenges and opportunities Bhima Vijayendran* A recent study estimates that, by 2025, over 15% of the three trillion dollar global chemical sales will be derived from bio-derived sources. Many of these bioproducts would be manufactured in bio-refineries by the deployment of rapidly emerging industrial biotechnology.It is expected that bioderived chemicals will come from three sources: direct production using conventional thermochemical and cataly- tic process, biorefining, and expression in plants. Direct production is already a rea- lity, as evidenced by the production of propane diol and polylactic acid from corn- derived glucose and others. There has been recent commercialization of bio-deri- ved plasticizers for polyvinyl chloride, polyester resins for coatings and inks, bio- polyols for urethane foams and others based on vegetable oil and carbohydrate renewable sources. Chemical biorefineries, on the other hand, based on various platforms such as carbohydrate/ cellulose, oil, and glycerin, a co-product of biodie- sel production, and algae are in the pilot stage. Chemicals expressed in genetical- ly enhanced plants to accentuate target functionalities such as primary hydroxyls, oxirane and others are in the discovery phase and furthest from commercializati- on. This paper highlights some of the recent developments and trends in each of the three waves for bioderived chemicals. Further, it also covers some of the suc- cesses in the commercialization of bioproducts, lessons learned, and challenges ahead for the nascent chemical biorefineries. * Battelle Science & Technology Malaysia, Sdn Bhd (809178-W) GTower, Suite 15.02 199 Jalan Tun Razak 50400 Kuala Lumpur, Malaysia [email protected] Journal of Business Chemistry 2010, 7 (3) © 2010 Institute of Business Administration Bio products from bio refineries - trends, challenges and opportunities 109
Transcript of Commentary - businesschemistry.org · Biodiesel → Intermediate ... It is worth noting that there...
Introduction
Arecent report (C&News,2009) estimates over$100 billion of the current global chemicalsmar-ket, about 3%, are derived from either bio-basedfeedstock or fermentation or enzymatic conver-sionor combinationof them.This report projectedthat the share of bio-derived chemicals wouldgrow to about 15% of global chemical sales by2025.There are several drivers for the interest andgrowth of bio products in themarketplace.A fewthat are worthmentioning include the availabi-lity of cost effective technologies includingnovelfunctional building blocks and improvedproces-ses, concerns about long term sustainability andprice volatility of fossil-based feedstock, a morebenign footprint on the environment, and con-sumer interest in greenproducts andpublic poli-cy.Many large and established chemical andbio-
technology companies aswell asnumerous smal-ler startup and venture companies are activelyinvolved in the development and commerciali-zation of bioproducts from a variety of renewa-ble biomass sources. These companies are tryingto followa bio-refinerymodel, similar to currentpetrochemical refineries,which co-produce largevolume commodity fuels and high value chemi-cals.
This paper covers the following topics relatedto these emerging technologies:
Various bio refinery modelsConversion technologies
First wave of bioproducts by thermo.. .chemical/catalytic conversion of bio-.. .derived feedstockBio feedstock platformsSecond wave of bioproducts by bioche
CommentaryBio products from bio refineries -trends, challenges and opportunities
Bhima Vijayendran*
A recent study estimates that, by 2025, over 15% of the three trillion dollar globalchemical saleswill be derived frombio-derived sources.Many of these bioproductswould be manufactured in bio-refineries by the deployment of rapidly emergingindustrial biotechnology. It is expected that bioderived chemicals will come fromthree sources: direct production using conventional thermochemical and cataly-tic process,biorefining,and expression in plants.Direct production is already a rea-lity, as evidenced by the production of propane diol and polylactic acid from corn-derived glucose and others. There has been recent commercialization of bio-deri-ved plasticizers for polyvinyl chloride, polyester resins for coatings and inks, bio-polyols for urethane foams and others based on vegetable oil and carbohydraterenewable sources. Chemical biorefineries, on the other hand, based on variousplatforms such as carbohydrate/ cellulose, oil, and glycerin, a co-product of biodie-sel production, and algae are in the pilot stage. Chemicals expressed in genetical-ly enhanced plants to accentuate target functionalities such as primary hydroxyls,oxirane and others are in the discovery phase and furthest from commercializati-on. This paper highlights some of the recent developments and trends in each ofthe three waves for bioderived chemicals. Further, it also covers some of the suc-cesses in the commercialization of bioproducts, lessons learned, and challengesahead for the nascent chemical biorefineries.
* Battelle Science & TechnologyMalaysia, Sdn Bhd (809178-W) GTower, Suite 15.02 199 Jalan TunRazak 50400 Kuala Lumpur,Malaysia [email protected]
Journal of Business Chemistry 2010, 7 (3) © 2010 Institute of Business Administration
Bio products from bio refineries - trends, challenges and opportunities
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mical conversion technologiesThird wave of bioproducts from genetic-.ally engineered plants with designed
.......... ..functionality of bio-monomers/building
............blocksSome challenges and opportunities for
....bio refineries
Various bio refinery models
There are various bio refinery models underdevelopment,most of which differ based on thebiomass source.Apalmplantation-basedbio refi-nery is shown in Figure 1.
The concept of palm-based bio refinery (andothers such as cornwetmill, sugar cane,and soy-bean) is quite simple and similar to the currentpetroleumrefineries.Biomass is converted to fuels(biodiesel from palm oil and bioethanol fromlignocellulosic contained in the feedstock, in thiscase empty fruit bunches, fronds,etc. that are resi-dues from palm oil processing) and value addedchemicals. In a typical palm plantation, besides
the oil and lignocellulosic biomass sources, thereis some activity to convert palm oil mill effluent(POME) to high value chemicals and biogas. Inthe case of cornwetmill and sugar cane planta-tions, biomass is converted to fuel (mostly bioethanol) and chemicals suchas polyols,acids,andothers. Onemajor difference between a bio refi-nery and petroleum refinery is that one of themainproduct fromabio refinery—at least for thefirst generation ones based on palm, corn, andsugar cane—is food forhumansandanimals.Thisis an important consideration and challenge andhas created a serious debate as to the sustaina-bility of first generation bio fuels in particular,and to a lesser extent for smaller volumebio pro-ducts. Technologies are being developed to useco-products from the first generation bio refine-ries that are not targeted for food and feed. Toaddress this problem more directly, the trend isto develop non-food energy crops such as jatro-pha, switchgrass,andothers as thebiomass sour-ce for future bio refineries. The general consen-sus is that the bio refineries will initially focus
Bhima Vijayendran
Journal of Business Chemistry 2010, 7 (3)© 2010 Institute of Business Administration
Figure 1 Emerging palm biorefinery concept
Fertilizers
HHaarrvveessttiinngg CCrruusshhiinngg RReeffiinniinngg
POME
Biocomposites Fuels
Refined
→
→
→ →
Biogas fuelPlastics
Chemicals
Residues andbyproducts Final Products
FermentationGasificationOthers
Various routes
Chemicals
→ →
→
Biodiesel
→
Intermediatestreams
FuelsChemicalsCoatingsAdhesivesFoams
FoodsSoaps
Cosmetics
→ → →
→
→
Glycerine
EFBFronds
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on large volume fuels followed by high value che-micals similar to the evolution of petrochemicalrefineries.
First wave bioproducts
Many first wave bioproducts are already inthe marketplace and are finding applications inmyriad end uses. These bioproducts are derivedfrom thermochemical conversion of new biomonomers or building blocks. Products often fallin two categories, namely, the ones that are che-mical replacement for petroleum-derived chemi-cals such as ethylene or lactic acid or functionalequivalent of existing chemicals. The main driverfor successful first wave bio products is the com-petitive cost of bio-derived feedstock comparedto the current petroleum counterpart that is beingreplaced. This is very true for bio products suchas bio ethylene derived from sugar cane or bio 1,3-propanediol that are targeted to replace corres-ponding petroleum derived products.
A few of the first wave bio product initiativesare captured in Figure 2.
It is worth noting that there are other projectssuch as the propylene glycol plant to be commis-sioned by Archer Daniel Midland (ADM) shortlyand the polyvinyl chloride (PVC) by Solvay Indu-pa in Brazil from bio based feedstock (Martinzand Quadros, 2007).
Bio feedstock platforms
The bio feedstock platform for the producti-on of bio products is mainly focused on the fol-
lowing chemical functionalities.
VVeeggeettaabbllee ooiill//ffaattttyy aacciidd eesstteerrss ooff ggllyycceerrooll
Vegetable oils and fats provide useful chemi-cal functionalities such as unsaturation and estergroups for further modifications using conven-tional schemes such as hydrogenation, selectiveoxidation, epoxidation , meta thesis reaction andothers to introduce functionality of value in diver-se applications such as plasticizers, coatings, adhe-sives, polymers, composites, etc. Several bio pro-ducts such as bioplasticizers for PVC (Vijayendran,2005), bio toners (Vijayendran, 2008), biopolyols(Benecke et al.; 2008) based on this approach havebeen commercialized recently.
SSuuggaarr--bbaasseedd ppllaattffoorrmm
Platforms based on sugars (Werpy and Peter-sen, 2004) have been deployed to create acidssuch as succinic acid and convert the acid to highvalue chemicals such as 2- pyrrolidone, 1,4-buta-nediol, tetra hydrofuran and others.
More recently cellulosic feedstock (Zhang etal., 2009) has been converted to 5-hydroxymethylfurfural (HMF) using some novel catalysts andionic liquids as platform chemical to make a varie-ty a high value chemicals derived from petroleumsources, as shown in Figure 3.
GGllyycceerriinnee PPllaattffoorrmm
Figure 4 shows bio products derived from crudeglycerine, a co-product of biodiesel production.
Journal of Business Chemistry 2010, 7 (3) © 2010 Institute of Business Administration
Bio products from bio refineries - trends, challenges and opportunities
DDuuPPoonntt BBiioo--PPDDOO((SSeerroonnaa®®))
NNaattuurree WWoorrkkssTTMMPPLLAA
BBrraasskkeemmBBiioo EEtthhyylleennee
PPllaanntt ssccaallee 45kTA 140kTA 200kTA
FFeerrmmeenntteedd pprroodduuccttss 1,3- Propanediol Lactic acid Ethanol
KKeeyy pprroocceesssseessFermentation,Cendensation,Polymerisation
Fermentation,Oligomerization,Ring-Closing &Ring Opening,Polymerizsation
Fermentation,Hydratation,Polymerization
IInniittiiaall pprroodduucctt PDO/TPACopolymer Polylactic acid
Ethylene,Polyethylene,Copolymers
FFlleexxiibbiilliittyy Moderate Low High VVAAMM
VVCCMM
EEOO
EEtthhyylleennee
PPEE
SSttyyrreennee
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Figure 2 Summary of the first wave of bio-derived plastics
Bhima Vijayendran
Journal of Business Chemistry 2010, 7 (3)© 2010 Institute of Business Administration
Figure 3 Derived from cellulosic biomass, 5-hydroxymethylfurfural (HMF) can be converted into many types of compoundsnow obtained from petroleum sources
Figure 4 Example platform production of bio products derived from crude glycerine
2-Methylfuran
2,5-Bis(hydroxymethyl)furan
Levulinic acid
Formic acid
2,5-Dimethyltetrahydrofuran
2,5-Dimethylfuran
2,5-Furandicarboxylic acid
5-Hydroxymethylfurfural→
→
→
→
→
→
Biodiesel/ BioethanolPlantrs
CCrruuddee ggllyycceerrooll
MMiiccrroobbiiaall cceellll ffaaccttoorryyby
-High throughput screening-Metabolic engineering
BBiioommaassss
FFuueellss-Ethanol-Butanol-H2
-Biogas-Nitrogen source
-Anaerobic condition (CO2 or N2)
CChheemmiiccaallss-1,3-Propanediol-Acetic acids-Butyric acid-Lactic acid-Formic acid-Propionic acid-Succinic acid
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2-Hydroxymethylfuran
There have been recent activities to convertabundant and low cost lignin to value added che-micals and fibers (Baker, 2009).
Recent commercialization efforts of first wavebioproducts have clearly shown that it is impor-tant that the technology is proven at the pilotscale and the economics are competitive with thepetroleum products. In many cases, such as in bioplasticizers for PVC and biotoners for office copiersand printers, the bio product replacements havefunctional attributes that are of value and notavailable from current petroleum products. In thecase of bio plasticizers, it is shown that one of thenew bio plasticizers, reFlexTM 100, has significant-ly better thermal stability, lower plasticizer migra-tion, and improved plasticization efficiency com-pared to industry standard (butyl benzyl phtha-late [BBP]) and a petroleum-based phthalate repla-cement (DINCH from BASF), as shown in Figure5.
Plasticization efficiency and thus lower uselevel with no known health concerns comparedto the petroleum based phthalate plasticizers,besides being “green” and environmentally friend-ly. See Table 1 for some comparative data of reFlex™100 bioplasticizer from PolyOne and the indus-try control, butyl benzyl phthalate (BBP).
In the case of bio toners, the bioproduct repla-cement has lower fusion temperature and easierrecycling of office waste paper (Vijayendran, 2008).The message that is becoming clear is that anynew bio products that are targeted to replace exis-ting petroleum-derived products should be ableto compete on cost and performance. Just being“green” and bio-derived from a sustainable sour-
ce are not enough to be accepted in the market-place.
Second wave bio products
The second wave bio products involving theconversion of bioderived sugars, cellulosics andoils by biochemical routes are in the advancedR&D and early pilot scale phases. Biochemicalprocessing using advances in metabolic enginee-ring and separation technologies to produce highvalue chemicals have made great strides in thelast few years. Bioprocessing tend to have the fol-lowing attributes compared to conventional ther-mo chemical conversion technologies:
Lower yieldsFairly dilute solutions with lower concentra-tions of activesMost reactions are done at ambient tempera-ture and pressure thus offering processes withpotential lower capital and operating invest-mentsMicroorganisms have several pathways tomake the same products and rapid screeningtools have helped to design metabolic path-ways to achieve high yields of target molecu-lesMost of the initiatives in the second wave bioproducts are in the advanced R&D or pilot scale.Major milestone is to demonstrate commer-cial viability of many of the technologies thathave shown R&D feasibility in the laborato-ry scale.
Journal of Business Chemistry 2010, 7 (3) © 2010 Institute of Business Administration
Bio products from bio refineries - trends, challenges and opportunities
Figure 5 Improved thermal stability of reFlex™ 100, a bio-derived green plasticizer, compared to butyl benzylPhthalate (BBP) plasticizer, and diisononylcyclohexane-1,2 dicarboxylate (DINCH), a petroleum-based non-phthalate plasticizer. Test conducted on heat stability in a metastat oven set to 375 degrees for 5-to-60 minutes.
BBBBPP
rreeFFlleexx 110000
DDIINNCCHH
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A few of the players that are active in thesecond wave bio product development and com-mercialization are shown in Table 2.
It will be interesting to watch over the nextseveral years how successful the second waveproducts from these companies are going to bein the marketplace.
It is worth mentioning here that there areseveral algae-based initiatives to make biofuelsand high value chemicals such as acids, alcohols,esters etc (Solix Biofuels.com). It should also bementioned that there is a joint venture betweenADM and Metabolix to produce poly hydroxylalkanoates, a polyester biopolymer with someinteresting properties (Chen, 2010).
Third wave bio products
Third wave bio products derived from plantexpression through genetic engineering to pro-duce chemicals with designed functionality arestill in the early discovery stage and furthest fromcommercialization. The work on high oleic acidoils is perhaps furthest along in terms of com-mercialization. There are several patents descri-bing the use of such high oleic acid oils in seve-ral industrial applications such as inks, lubricants,etc. (Knowlton, 1999). Some early work has shownthe feasibility of introducing primary hydroxylfunctionality in vegetable oils such as canola.About 12% riconelic acid has been expressed in
conventional canola seed (Grushcow, 2007). Pri-mary hydroxyl functionality from such modifiedoils has several useful functionalities and attri-butes of interest in lubricant, coating and poly-mer applications. Recent work at CSIRO, Austra-lia (Green et al., 2009) has shown the feasibilityof expressing high levels of epoxy functionalityin some native oil seeds. A crop producing epoxyoil would be an interesting replacement for epo-xidized oils produced by the convention per acidroute. The same group has also expressed acety-linic functionality in plant oils with the potenti-al provide useful reactivity and functionality ofvalue in several high value chemical applicati-ons.
Summary
Use of bio products is growing with the firstwave products derived from thermochemical con-version of bio-derived building block taking thelead in commercialization. Second wave bio pro-ducts produced by metabolic engineering andbioprocessing technologies are in the pilot scale.Third wave bio products based on plant expres-sion are in the discovery phase. Bio refineriesbased on a variety of biomass feedstock are stillin the nascent stage and will require some timeto fully develop. Continued R&D investment toimprove the technologies to provide cost effecti-ve solutions is very much needed. Also, establish-
Bhima Vijayendran
Journal of Business Chemistry 2010, 7 (3)© 2010 Institute of Business Administration
Table 1 Benefits of reFlex™ 100 in plastisol and flexible PVC applications
FFeeaattuurree BBeenneeffiitt
Bio-derived Allows the incorporation of high level of renewable content
Improved air releaseReduced evacuation timeImproved productivityReduced defect rate
Greater efficiency Reduced usage level
Fast gelation and fusionFast processingLow fusion temperatures possible
Lower paste viscosity Easier material handling
Imparts excellent thermal stabilityReduction of heat stabilizers - lower costMore robust performance
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ment of supply chain of feedstock as well as com-patibility with existing infrastructure of the wellestablished petrochemical industry is expectedto facilitate commercialization of bioproducts. Itis expected that bio products from bio refinerswill continue to grow and compliment the petro-chemical refineries to serve the global chemicalsmarkets.
RReeffeerreenncceess
Baker,F.S., Low Cost Carbon Fiber from Renewable Resource.,EERE, U.S. Dept of Energy Project ID # lm_03_baker
Benecke, H., Vijayendran, B.R., Garbark, D. and Mitchell, K.(2008): Low Cost Highly Reactive Biobased Polyol—A Co-Product of Emerging Bio Refinery Economy., Clean Jour-nal, 3366 (8), p. 694.
C&News, July 2009, p. 26-28.C&News, Bio Refineries, Oct 12, 2009, p. 28-29.Chen, G.Q., Industrial Production of PHA., Plastics from Bacte-
ria., Microbiology Series Vol. 1144, 121-132,Choi, W.J. (2008): Glycerol Based Bio refinery for Fuels and
Chemicals, Recent Advances on Biotechnology, 22 (3), p.174.
Gray, J. (2009): Personal communication from PolyOne, Cleve-land, OH.
Green, A., O’Shea, M., Lawrence, L. and Begley, C. (2009): Bey-ond Biodiesel., Inform, 2200 (6), p. 345.
Grushcow, J. (2007): New Opportunities in Oil Seed Enginee-ring., available at http://www.linnaeus.net, accessed,
2009 Knowlton, S. (1999): U.S. Pat 5981781, Du Pont Company.Martinz, D. and Quadros, J. (2007): Presentation at Brighton
Conference, Brighton, U.K.Vijayendran, B.R. (2005): Emerging Opportunities and Chal-
lenges for Soybean oil –derived Industrial Products.,Inform, 1166 (10), p. 659.
Vijayendran, B.R. (2008): Presidential Green Chemistry AwardInvited Lecture, Washington, June 2008.
Werpy, T. and Petersen G. (2004): USDOE’s Top Sugar Deri-ved Building Blocks, available at http://www.nrel.gov/docs/fy04osti/35523.pdf, accessed 2009.
Zhang, Z.C. (2009): Single Step Conversion of Cellulose to 5-Hydroxyl Methyl Furfural (HMF) - a versatile PlatformChemical., Applied Catalysis. A 3366, p. 117
Journal of Business Chemistry 2010, 7 (3) © 2010 Institute of Business Administration
Bio products from bio refineries - trends, challenges and opportunities
Table 2 Second wave bio products other than ethanol and biodiesel
CCoommppaannyy PPrroodduucctt CCoonnttaacctt
Gevo Isobutanol www.gevo.com
Verdezyne Adipic acis verdezyne&Schwartz-pr.com
Myriant Technologies Succinic acid www.myriant.com
Opexbio Acrylic acid www.opxbio.com
SyntheZyme w-hydroxyfatty acids [email protected]
Virent BioForming process for various chemi-cals www.virent.com
Zeachem Ethyl acetate/ ethanol www.zeachem.com
LS 9, Inc Hydrocarbon/ fuel www.LS9.com
Genecor/ Good Year Isoprene www.genecor.com
Genomatica 1,4 butanediol www.genomatica.com
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