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Table 1 Summary of the chemicals and materials analysed

From: A review on commercial-scale high-value products that can be produced alongside cellulosic ethanol

CompoundClassic production routeBio-based routePrice (per ton)Market (per year)Market volume (tonnes per year)UsesChallenges for integration
1,2-ButanediolCatalytic or steam cracking of gas (ethane, propane, butane) and/or naphtha [175]Hydrogenation of sorbitol [176]$2666 [174]$4 billion [174]1.5 million [174]Production of adhesive resins or as a solvent, coolant, refrigerant, hydraulic fluid, or fine chemical raw material. [173]Relies on the successful production sorbitol
1,3-PropanediolPro Degussa’s technology [184, 185], hydrogenation of 3-hydroxypropionaldehyde [186]Fermentation of sugars [198, 199, 203]$1450 [190]$310 million [181]146,000 [182]Production of polyesters, polyethers, and polyurethanes [182, 183]Separation and purification of the cellulosic sugars stream
Optimization of microorganism
1,4-ButanediolReppe process [198], hydrogenation, and hydrolysis [206, 208]Hydrogenation of SA [209], and fermentation of sugars [210]$2660 [205]$5690 million [538]2 million [205]Manufacture of polymers, solvents, and chemicals. [206, 207]Relies on SA
Optimization of microorganism and catalysts
2,3-ButanediolChlorohydrination and hydrolysis [539]Catalytic hydrogenation [223] and fermentation of sugars [225,226,227,228,229]$10,000 to 50,000 [222]$43 billion [220, 221]32 million [220, 221]Production of printing inks, perfumes, fumigants, moistening and softening agents [219]Separation and purification of the cellulosic sugars stream
AcetaldehydeDehydrogenation or oxidation of ethanol, addition of water to acetylene, partial oxidation of hydrocarbons, and direct oxidation of ethylene [251,252,253]Oxidation of ethanol [252, 255]$1005 [540]$1.26 billion [250]1.28 million [541]Manufacture of acetic acid, perfumes, dyes, and drugs, as a flavoring agent and as an intermediate in the metabolism of alcohol [249]Competitive prices against fossil-based equivalent
Acetic acidCarbonylation with Rh-catalyzed Monsanto or Ir-catalyzed Cativa process [258]Catalytic oxidation of ethanol [261, 263], fermentation of ethanol or sugars [264]$617 [162]$8373 million [162]8.3 million [161]Applications include: foam rubber, wood gluing, emulsifiers, cement coatings, and desalination membranes [142]Separation and purification of the cellulosic sugars stream
Competitive prices against fossil-based equivalent
Acetic anhydrideAcOH dehydration [270], acetone cracking [271], acetaldehyde oxidation [272], and methyl acetate carbonylation [273]AcOH dehydration [270]$797 [542]$635.9 million [543]2.7 million [269]Use in the preparation of modified food starch and acetylation of monoglycerides, and in the manufacture of pesticides and herbicides [268]Relies on AcOH
Competitive prices against fossil-based equivalent
AcetoneThermal decomposition of calcium acetate, dehydrogenation of isopropyl alcohol or cumene oxidation [264, 277]Fermentation of sugars [277] and ABE process [264, 281]$1210 [205]$7700 million [162]6.1 million [544]Production of acrylic plastics, signs, lighting fixtures and displays, and Bisphenol A (BPA), and as a solvent in multiple products, such as paints, cleaning fluids, and adhesives [276]Produced alongside ethanol and butanol
Addressed inhibitors and toxic compounds
ButanolOxo reaction of propylene [280]ABE process [264, 281]$1463 [205]$4200 million [162]3.4 million [545]Use in the manufacture of adhesives, sealant chemical, paint additives, coating additives, plasticizer, and cleaning products [280]Produced alongside ethanol and acetone
Detailed market analyses needed to define competitiveness against ethanol
EthanolDirect or indirect catalytic hydration of ethylene, homologation of methanol, and carbonylation of methanol and methyl acetate [546]Fermentation of starch, sugar, and other carbohydrates [130]$514 [547]$64.52 billion [548]80.88 million [549]Manufacture of adhesives and sealant chemicals, beverage ingredients, food products and use as fuels and fuel additives [546]Competitive prices against fossil-based equivalent
Elevated production costs
Ethyl acetateFisher esterification, dehydrogenation of ethanol, and Tischenko reaction [302]Dehydrogenation of ethanol [303]$1434–1507 [301]$1.33 billion [550]3.2 million [300]Used in the production of inks, adhesives, car care chemicals, plastic, and as a synthetic fruit essence, flavour and perfume in the food industry [299]Competitive prices against fossil-based equivalent
Ethyl LactateEsterification of LA with fossil based ethanol [312], and esterification of ammonium lactate [314]Esterification of LA with bio-based ethanol [312]$3300–4400 [312]$81 million [551]1.2 million [161]Potential to replace conventional petroleum-based solvents such as toluene, methyl ethyl ketone, and N-methyl-pyrrolidone [198]Relies on LA and ethanol
High dependency on demand and price of raw materials
Ethyl tert-butyl etherCatalytic reaction of fossil based isobutene and ethanol [324, 325]Catalytic reaction of fossil based isobutene and bioethanol [324, 325] [327]$856–906 [552]$2.13 billion [553]3 million [553]Use as gasoline additive [321]Relies on isobutene and ethanol
Future demand
Competitive prices against fossil-based equivalent
EthyleneSteam cracking of hydrocarbons [142]Dehydration of ethanol [328]$1370 [162, 205]$140,000–203,000 million [162, 205]146.5 million [554]Use to manufacture plastics, e.g., HDPE, LDPE, LLDPE, PVC, and PET [161]Relies on ethanol
Depends on the ethanol price and stock
Ethylene glycolHydrolysis of ethylene oxide. [142, 336]Hydrogenation of sorbitol [337]$1144 [205]$28.58 billion [555]34.8 million [555]Manufacture of antifreeze, hydraulic brake fluids, industrial humectants, printer’s inks, and in the synthesis of safety explosives, plasticizers, synthetic fibers [335], and MEG [161]Relies on sorbitol
Competes against fossil-based equivalent
Ethylene propylene diene monomerFrom fossil based ethylene using Ziegler–Natta olefin polymerization [346]From bio-based ethylene using Ziegler–Natta olefin polymerization [346]$2000 [556]$4203 million [556]1.32 million [557]Use in the automotive, construction industry, and in the manufacture of oil additives [342]Relies on ethylene
Requires favorable rubber market
FurfuralAcid hydrolysis of pentosan [353]$2200 [351]$625.5 million [287]270,000 [198]Apply in the production of specialist adhesives, and as flavor compound [350], it is a key bio-based platform chemical that can be used to replace oil-based chemicals [142]High degradation of cellulose during furfural processing
Further R&D needed
Furfuryl alcoholHydrogenation of furfural [162]$1500 [558]$376.9 million [558]300,000 [559]Use as an additive or solvent in the production of resins, as a chemical intermediate to manufacture lysine, vitamin C, lubricants, and dispersing agents [362]Relies on furfural
Successful separation of pentose- and hexose-sugars
Glutamic acidFermentation of sugars [142, 373]$1400 [560]$8.5 million [561]200,000 [142]Use as thickener, humectant, cryoprotectant, drug carrier, biodegradable fibers, highly water absorbable hydrogels, biopolymer flocculants, and animal feed additives [372]Volatility of corn and coal prices
Separation and purification of the cellulosic sugars stream
IsobutanolHydrogenated of butyraldehyde [386], LP OxoSM Process [387],, and Reppe carbonylation [387]Fermentation of sugars, [389] and consolidated bioprocessing (CBP) [392]$1530 [205]$775.0 million [562]500,000 [205]Precursor of various isobutyl esters, chemical intermediate, pharmaceuticals, and automotive paint cleaner additive [383], was well as being use as a fuel [384]Separation and purification of the cellulosic sugars stream
Itaconic acidDistillation of citric acid [398]Fermentation of sugars [398]$1900 [162]$79.0 million [162]40,000 [563]Production of lubricant additives, surface active agents, dye intermediates, plastics, synthetic rubber, and MMA [162]Niche market with low demand
Downstream conversion to MMA not commercial
Commercial production stopped
Lactic acidHydrolysis of lactonitrile by H2SO4 or by HCl [408]Fermentation of sucrose [408]$1300–2300 [407]$2.22 billion [564]120,000 [407]Apply in the food and beverage sector as a preservative and pH adjusting agent, and as a starting material in the production of lactate ester [161]Technical barriers similar to 2G ethanol.
Separation and purification of the cellulosic sugars stream
LactideDepolymerization of OLLA. [418]$781.81 million  [565]Use as an additive for the conservation of milk and meat-based products, as a pH regulator for tofu, soybeans, and dairy products, and as a combustion improvement agent for coal and oil [416]Relies on LA
LysineFermentation of sugars [161, 426, 427]$1200 [566, 567]$745.2 million [568]1.7 million [423]As supplement to optimize animal growth [422]Removal of inhibitors in the cellulosic sugars stream
Microfibrillated celluloseSuccessive refining follow by enzymatic hydrolysis and homogenization [435]$232 million [569]10,000 [440, 449]Use in the manufacture of nanocomposites, packaging, coating, and dispersion technology [436, 439]Large energy consumption
PolyethyleneDehydration of fossil based ethanol to ethylene and subsequent polymerization [454]Dehydration of bio based ethanol to ethylene and subsequent polymerization [454]$1676 [162, 205]$163 billion  [570]200,000 [162, 338]Manufacture of plastic bags, plastic films, geo-membranes, bottles, and tubes [162, 205]Relies on ethylene production
Price difference between fossil and bio-based PE
Polyethylene glycolAnionic ring opening polymerization of ethylene oxide [457], and polycondensation fossil based 1,3-PDO [458]Polycondensation of bio-based 1,3-PDO [199, 458]$2000 [571]$150 million [572]2.2 million [573]Suitable to produce copolymers, e.g., linear, branched, star-shaped, and comb-like PEGs [457]Relies on the success of bio 1,3-PDO
Development of efficient microorganisms
Polylactic acidPoly-condensation of fossil based lactic acid [461], and ring-opening polymerization (ROP) of dimeric lactide [462]Poly-condensation of bio-based lactic acid [461]$2300 [574]$950.7 million [575]180,000 [576]May replace conventional synthetic polymers, especially in packaging. It is also used as insulation foam, for automotive parts, and fibres [162]Depend on the commercial production of bio-LA
Need competitive prices against fossil-based PLA
Polytrimethylene terephthalateTransesterification using fossil based 1,3-PDO [465]Transesterification using bio-based 1,3-PDO [465]$2033 [189]194,120 of bio-based PTT [577]Use as thermoplastic fibers or film [199, 467]Relies on the success of bio 1,3-PDO
Requires that the industry moves towards replacing conventional polyesters
Propylene glycolHydration of propylene oxide, catalytic hydrogenolysis of glycerol [198]Hydrocracking of sorbitol [142, 471, 472], hydrogenolysis of xylitol [163], and hydrogenation of LA or lactates [142]$1530 [205]$3.91 billion [578]2 million [579]Used in the production of unsaturated polyester resins, coolants and antifreeze, aircraft de-icing fluid, heat transfer fluids, paints, and coatings [142]Due to the abundant production of glycerol, PG production will be most likely based on glycerol
SorbitolHydrogenation of glucose [142, 471, 472], fermentation of fructose and glucose [488], and one-pot conversion [489]$650 [162]$107 million [162]164,000 [162]Used as sweetener, thickener, humectant, excipient, and dispersant in food, cosmetic, and toothpaste [142]Separation and purification of the cellulosic sugars stream
Isolation of glucose from the cellulosic sugars stream
SqualeneExtracted from shark liver oil [505]Fermentation of glucose [506, 510]$250,000 [503]$ 166.1 million [580]2400 [504]Applications in the manufacture of fine chemicals, magnetic tape, emollient in cosmetics and pharmaceuticals, as well as an additive in animal feed [503]Isolation of glucose and removal of inhibitors
Succinic acidHydrogenation of maleic anhydride or maleic acid [198]Fermentation of sugars [514, 518]$2500 [514]$131.73 million [581]50,000 [582]Niche applications such as personal care products and food additives to large volume applications such as biopolymers, plasticizers, polyurethanes, resins, and coatings [162]Develop of efficient and inhibitor resistant strain
Isolation of glucose
TerpenesExtracted or steam distilled [522], as a by-product of naphtha or oil cracking in the production of ethylene [524]Microbial fermentation [524, 525]$7000 [583]$650 million [523]247,100 [583]Used to create fine perfumes, to refine the flavor and aroma of food and drinks, and to produce medicines of plant origin [522]Isolation of glucose and removal of inhibitors
XylitolHydrogenation of xylose [529]Fermentation of xylose [532]$3900 [162]$624 million [162]190,900 [584]As a diabetic sweetener xylitol is used in the food (confectioneries and chewing gums), odontological, and pharmaceutical sectors [162]Efficient isolation of xylose from the cellulosic sugar stream