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
Compound | Classic production route | Bio-based route | Price (per ton) | Market (per year) | Market volume (tonnes per year) | Uses | Challenges for integration |
|---|---|---|---|---|---|---|---|
1,2-Butanediol | Catalytic 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-Propanediol | Pro Degussa’s technology [184, 185], hydrogenation of 3-hydroxypropionaldehyde [186] | $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-Butanediol | Reppe process [198], hydrogenation, and hydrolysis [206, 208] | $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-Butanediol | Chlorohydrination and hydrolysis [539] | Catalytic hydrogenation [223] and fermentation of sugars [225,226,227,228,229] | $10,000 to 50,000 [222] | Production of printing inks, perfumes, fumigants, moistening and softening agents [219] | Separation and purification of the cellulosic sugars stream | ||
Acetaldehyde | Dehydrogenation or oxidation of ethanol, addition of water to acetylene, partial oxidation of hydrocarbons, and direct oxidation of ethylene [251,252,253] | $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 acid | Carbonylation 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 anhydride | AcOH 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 |
Acetone | Thermal decomposition of calcium acetate, dehydrogenation of isopropyl alcohol or cumene oxidation [264, 277] | $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 | |
Butanol | Oxo reaction of propylene [280] | $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 | |
Ethanol | Direct 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 acetate | Fisher 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 Lactate | Esterification 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 ether | Catalytic 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 |
Ethylene | Steam cracking of hydrocarbons [142] | Dehydration of ethanol [328] | 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 glycol | 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 monomer | From 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 |
Furfural | – | Acid 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 alcohol | – | Hydrogenation 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 acid | – | $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 | |
Isobutanol | Hydrogenated 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 acid | Distillation 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 acid | Hydrolysis 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 |
Lactide | Depolymerization 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 | |
Lysine | $745.2 million [568] | 1.7 million [423] | As supplement to optimize animal growth [422] | Removal of inhibitors in the cellulosic sugars stream | |||
Microfibrillated cellulose | – | Successive refining follow by enzymatic hydrolysis and homogenization [435] | – | $232 million [569] | Use in the manufacture of nanocomposites, packaging, coating, and dispersion technology [436, 439] | Large energy consumption | |
Polyethylene | Dehydration of fossil based ethanol to ethylene and subsequent polymerization [454] | Dehydration of bio based ethanol to ethylene and subsequent polymerization [454] | $163 billion [570] | 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 glycol | Anionic ring opening polymerization of ethylene oxide [457], and polycondensation fossil based 1,3-PDO [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 acid | Poly-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 terephthalate | Transesterification using fossil based 1,3-PDO [465] | Transesterification using bio-based 1,3-PDO [465] | $2033 [189] | – | 194,120 of bio-based PTT [577] | Relies on the success of bio 1,3-PDO Requires that the industry moves towards replacing conventional polyesters | |
Propylene glycol | Hydration 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 |
Sorbitol | – | Hydrogenation 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 |
Squalene | Extracted from shark liver oil [505] | $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 acid | Hydrogenation of maleic anhydride or maleic acid [198] | $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 | |
Terpenes | Extracted or steam distilled [522], as a by-product of naphtha or oil cracking in the production of ethylene [524] | $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 | |
Xylitol | Hydrogenation 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 |