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Abstract:

Solvents used in many industries are currently derived from fossil fuels, which are limited resources, and their usage can cause an increased risk to health and environment. Hence the need to minimize their usage or replace them with renewable/bio-derived solvents. Solvents can be prepared from renewable sources such as agricultural crops or biomass, called bio-derived or bio-based, or simply, bio-solvents, to decrease the reliance on petroleum-based products. Renewable solvents thus generate lower Volatile Organic Compounds (VOC) emissions, are 100% biodegradable, easy to recycle, non-corrosive, non-carcinogenic, and non-ozone-depleting. These bio solvents are useable in a number of industries as well, as all the industries are now inclined towards sustainability.

Introduction:

Solvents, which are the key elements of many industries, are currently derived from fossil fuels. The usage of these solvents causes an increased risk to health and environment. Many solvents contain Volatile Organic Compounds (VOCs) and Hazardous Air Pollutants (HAPs) which, in the presence of sunlight and nitrogen oxides (NOx) lead to the emission of ground level ozone and thus, contribute to ozone pollution.[1] VOCs also cause the green-house effect. Hence, it is necessary to minimize their usage or replace them with renewable/bio-derived solvents.

Solvents can be prepared from renewable sources to decrease the reliance on petroleum-based products, which are a limited resource. The solvents prepared from renewable sources such as agricultural crops or biomass are called bio-derived or bio-based, or simply, bio-solvents. These renewable solvents generate lower VOC emissions, are 100% biodegradable, easy to recycle, non-corrosive, non-carcinogenic, and non-ozone-depleting. These bio solvents are used in a number of industries such as paints & coatings, pharmaceuticals, adhesives, home & personal care, industrial & domestic cleaners, plastics & polymers, agrochemicals, food & beverage, printing inks, cosmetics, petrochemicals and fuels.

Sources of bio-based solvents:

Natural sources that can be used for the production of bio-solvents include waste materials (agricultural, wood, and urban wastes, crop residues), forest products (wood, logging residues, trees, shrubs), energy crops (starch crops such as corn, wheat, and barley, sugar crops and grasses) and, aquatic biomass (Algae, water weed and water hyacinth). Biomass can be divided into three categories based on their chemical composition; namely, cellulosic biomass, starch and sugar-derived biomass (or edible biomass), and triglyceride-based biomass. A wide variety of solvents such as alcohols, ethers, acids, esters etc. are synthesized from different natural sources. A few examples of classes of bio-based solvents synthesized from biomass sources are shown in the figure below.[2]

Sources of bio-based solvents

A 10-step method was developed by the University of York, which encompasses a hierarchy of assessments and tests designed to help identify replacements of organic solvents and guide the development of new bio-based solvents. The method will not only indicate if a new solvent is functionally proficient (through a combination of in-silico modeling, property measurements and lab scale testing) but will also highlight potential health risks from the solvent under investigation. The detailed hierarchy of the method is shown below:[3]

Sources of bio-based solvents

Preparation methods of bio-based solvents:

Three major methods of preparing solvents from biomass are listed below:

a) Fermentation

b) Chemical transformation of biomass derivatives

c) Use of waste material from other processes.[4]

Some of the technologies and processes operating at commercial / demonstration scale are: (1) Solvay’s Augeo™ SL 191 renewable solvent, (2) Circa Group’s Furacell™ technology and process for making levoglucosenone (LGO) to produce dihydrolevoglucosenone (marketed as Cyrene™), (3) Sappi’s Xylex® technology and demonstration scale processes that aim to manufacture precursors for biosolvents and (4) Anellotech’s Bio-TCat™ technology and process for producing benzene, toluene and xylenes (BTX).[5]

Bio-Based Solvents

ALCOHOLS:
ABE (Acetone, Butanol, Ethanol)

Celtic Renewables Ltd. is the first company to produce biofuel from the by-products of the Scotch whisky industry. The bio-butanol produced can be a direct replacement for petrol and diesel, and can be used in the engines of any car without any modification.[6]

The company has two US patents that were granted in 2021 (US11198889B2, US11046977B2) for this process. The process involves manufacture of butanol/acetone by the fermentation of by-products produced in the manufacturing of malt whisky such as draff, pot ale and/or spent lees, biomass substrates, such as paper, sludge from paper manufacture and spent grains from distillers and brewers, and diluents, such as water and spent liquid from other fermentations. Butanol- and/or acetone-forming micro-organisms, particularly bacteria of the genus Clostridium, is used in fermentation.

bio-based solvents

The company is constructing its first state-of-the-art commercial processing plant at Caledon Green, in Grangemouth Scotland, to transform locally sourced low-value materials into low-carbon, high-value, sustainable bioproducts. The facility will process the residues from local distilleries to produce high-value sustainable biochemical products (Acetone, Butanol and Ethanol) that will displace existing petrochemicals.[7]

Caldic and Celtic Renewables signed an agreement in November 2021 to bring innovative bio-solvents, produced in Scotland, to the global market.[8]

Bio-BDOTM

(1, 4 butane Diol)

Genomatica created Bio-BDOTM (1, 4-butanediol) in 2008, from renewable feedstocks such as sugarcane and sugar beets, and other sources of carbohydrates, such as cor, through fermentation using mutants of E.coli. Bio-BDOTM is a key ingredient in a diverse range of products, from spandex to shoes to plastics in cars and electronics, made from plant sugars instead of petroleum.

bio-based solvents

In 2016, Novamont opened the world’s first bio-based plant using geno BDO™ technology. In 2021, Cargill and HELM, a family-owned company based out of Hamburg in Germany, partnered to enter into a joint venture Qore, which will focus on producing QIRA™, the next-generation 1,4-butanediol. Both companies are investing $300 million to build the first commercial-scale renewable BDO facility in the U.S. Genomatica licensed its BDO™ technology to the companies. After completion in 2024, the facility will be able to produce more than 65,000 tons of BDO per year.[9]

ESTERS:

Cyrene™ (Dihydrolevoglucosenone or 6,8-dioxabicyclo octanone) was developed by Circa Group in partnership with Professor James Clark, Ph.D., at the University of York’s Green Chemistry Centre of Excellence (GCCE). The synthesis involves two steps: The first is the Furacell™ process, in which a cellulosic raw material is converted to levoglucosenone (LGO). The next step is the hydrogenation of LGO to Cyrene™ through the use of a heterogeneous Pd catalyst.[10] Circa Group filed a patent application (WO2020037351A1), for the synthesis of levoglucosenone (LGO) from cellulosic material. The patent application discloses that the cellulosic material is wood in particulate form, wherein wood is dried to reduce its water content to less than 100%. A premix is formed by mixing particulate wood, water, acid, and a polar organic solvent. The pre-mix is fed into a pyrolysis reactor, such as a fluidised bed reactor, in which the pre-mix is fluidised by a fluidising gas. The reactor is maintained at a temperature between 250 and 450°C, and gaseous products and char are withdrawn from the pyrolysis reactor. The gaseous products containing Levoglucosenone and the polar organic solvent are condensed. The solvent is recycled to form further pre-mix.

bio-based solvents

bio-based solventsCyrene is an alternative solvent to Dimethylformamide (DMF), N-Methyl-2-pyrrolidone (NMP) and DCM. Cyrene™ was awarded the ‘European Bio-based Chemical Innovation of the Year’ award in 2017 and the ‘Environmental Leader’s Top Product of the Year’ award in 2019, in recognition of its credentials as a safer, greener alternative to petroleum-based solvents that can also have superior performance.[11]

The University of Manchester has successfully produced the highest quality conductive graphene ink using Cyrene® instead of NMP. Over the next 10 years, several millions of tonnes of spent batteries will need to be recycled. Cyrene™ is used to recover polyvinylidene fluoride (PVDF), a high-performance polymer widely used as a binder in Li-ion battery cathodes, in a sustainable way.[12] It is also used in the preparation of Poly (lactic-co-glycolic acid) nanoparticles as a drug delivery system for circumventing high viscosity and plasticizing effects.[13] It acts as a green alternative to DMSO for antibacterial drug discovery against ESKAPE pathogen and exhibits slightly more toxicity towards bacteria.[14] It is used in polymerization of various monomers using Cu (0) wire-mediated RDRP (reversible deactivation radical polymerization) without applying any external deoxygenation. It enables the synthesis of diblock and triblock copolymers.[15] It is used in amide coupling.[16] Future applications of LGO derivatives is predicted to be in pharmaceuticals, agrochemicals, graphene, electronics, batteries, paints and coatings, flavors and fragrances as well as polymers.

bio-based solventsRecently, in 2022, Circa partnered with Valmet for the targeted production of 1,100 tonnes of Cyrene™ by 2030, through the ReSolute project, by optimising the Furacell™ production process. The scale-up plant is situated in the Grand-Est Region (France).[17] Valmet is a developer and supplier of process technologies, automation, and services for the pulp, paper, and energy industries.

SoyGold® Soy Methyl EstersAGP chemPoint is the manufacturer of SoyGold® soy methyl esters, which are produced from natural whole soybean oil. Soybean oil-based methyl esters act as natural, multipurpose solvents. The main application of the solvent is its usage as a lubricity component in diesel fuel and also in cleaning. It efficiently acts as a solvent for industries such as printing, chemical formulating and adhesives. Different grades of Soy Methyl Esters are commercially available; these have found application in agriculture (as carriers in pesticides & adjuvants), the cleaning industry, water treatment, and soil and groundwater remediation.[18]

Agri-pure™:

Agri-pure™ is a product developed by Cargill, Inc. Agri-pure™ AP-406 is a rapeseed oil-derived methyl ester solvent. It is used as an alternative to white spirit, kerosene, liquid paraffin and other low-to-medium viscosity hydrocarbon oils. It is also compatible with many chlorinated and oxygenated solvents, so that a partial replacement of these solvents may also be possible in some cases.

The solvent has good rheological properties and printability. It is used in industrial degreasing, oil refinery CIP, removal of concrete stains, graffiti, varnish, adhesives, and hand cleaners. The fluid properties of Agri-pure™ AP-406 resemble light mineral oils. The solvent is used in the formulation of metal-working fluids, mold-release agents and textile lubricants. It can also be used in the production of sulphurised EP additives, and as a carrier fluid /compatibiliser for additive packages. Agri-pure™ AP-406 is used as an oil adjuvant, improving rain-fastness, softening waxy leaf cuticles and enhancing the activity of herbicides at low dosage.[19]

ChemPoint and Cargill, Inc. have recently (2022) signed an agreement to partner on the distribution, marketing, and sales of the naturally derived, plant-based rapeseed oil methyl ester Agri-Pure™ AP-406, in EMEA. Cargill will continue to develop and deliver innovative bio-solvents, while ChemPoint will provide the expertise and high service level in online marketing, supply chain, logistics and sales to expedite the delivery of Cargill Biosolvents.[20]

ETHERS:

SOLVONK4TM

Green Biologics and Kreussler Chemicals together developed this only bio-based patented (US8801807B2) solvent used in the drycleaning industry.[21] It is derived from corn and is biodegradable. It is the main solvent in the SYSTEMK4 drycleaning process for cleaning textiles, leather and furs. It is a halogen-free solvent with more than 99% purity, which has excellent cleaning performance and the cleaned textiles have a fresh scent.

bio-based solventsGreen Biologics used their patented fermentation (US20150368678A1) process, using the Clostridium saccharoperbutylacetonicum microorganism to convert feedstocks into the bio-based n-butanol. SOLVONK4TM is composed primarily of butylal, which is a diether acetal for which n-butanol is used as reactant. About 550 SYSTEMK4 cleaning machines have already been installed in over 20 countries. In addition to the environmental benefits, it has a unique cleaning power and is economical.[22]

HE-70S:

Developed by Braskem, HE-70S is the first partially renewable solvent made from sugarcane ethanol. It is part of the oxygenated solvents group. The solvent is sustainable, has low carbon footprint with outstanding performance, high relative evaporation rate (R.E.R.), low density and low surface tension. The solvent finds its application mainly in footwear, furniture, ceramics industry, ink and thinner industries. Braskem partnered with Dutch-based NXTLEVVEL Biochem in 2021, to study market opportunities for solvents made from renewable raw materials and also to launch more sustainable solvents in Latin America.[23]

FURANS:

EcoXtract®

Pennakem Europa, an affiliate of the Minafin Group, has developed an innovative, natural extraction process to extract oil, proteins and natural ingredients from plant seeds. The process involves the usage of bio-based solvent. WO2020128307, published in 2020, claims a method for producing a crude oil rich in polyphenols, starting from biological substrates, using 2-methyloxolane and water. This development is the result of a proposal submitted by a consortium of 5 partners. All are private-for-profit entities established within the European Union. The consortium includes Pennakem Europa (France), an affiliate of Minafin Group, and comprises Vivaorganic GmbH (Cloppenburg, Germany), De Wit Speciality Oils B.V. (De Waal, The Netherlands), New Holland Extraction Ltd (New Holland, United Kingdom) and Donal Murphy-Bokern (Lohne, Germany). The project is coordinated by Vivaorganic GmbH.[24]

The process is a substitute to petro-based extraction, which uses harmful hexane. The advantage of using EcoXtract solution is that it is a bio-based solution, and hence will reduce the carbon footprint of an extraction process. EcoXtract® uses bio-based liquid, made from corn cob or sugar cane bagasse (or other hemicellulose-rich streams such as rice husks or almond shells).[25]

Green Solvents

EcoXtract® has been awarded a 2.8 million EUR grant by the European Commission’s European Innovation Council to develop EcoXtract® as the extraction solution of choice for the global oil and protein sector. It is classified as a low toxicity solvent by the international pharmaceutical expert group ICH Q3C. It has earned the Certified Biobased Product label granted by the U.S. Department of Agriculture (USDA).[26] It has also received the “Solar Impulse Efficient Solution” Label, an award for clean and profitable solutions.[27]

Green Solvents

EcoXtract® solvent, 2-Methyloxolane, also known as 2-methyl tetrahydrofuran (2-MeTHF), is used as a green solvent for simultaneous production of soybean oil and defatted meal.[28] It is used as a sustainable lipophilic solvent to substitute hexane for green extraction of natural products.[29] It is also used in the preparation of oils for cosmetic products complying with the Cosmos standard. The solvent is used in green extraction of aromas from Hops (Humulus lupulus L.), extraction of phenolic acid antioxidants (hydroxybenzoic & hydroxycinnamic acids) from aqueous environments, and bioactive lipid extraction from black cumin and basil seeds rich in compounds relevant to the human diet. Recently, the European Food and Safety Authority (EFSA) has given acceptance for the usage of methyloxolane in food processing.

Pennakem Europa, together with INRAE (National Research Institute for Agriculture, Food and the Environment) and Avignon University, was granted financial support of nearly five million euros by ADEME (French Environment and Energy Management Agency) in Dec 2021, to develop the project.

AstroBioTM Green Solvents:

ASTROBIO™ is an Italian industrial firm, developing bio-based solvents since 2006. Its main vision is to replace all traditional petrochemical solvents with green solvents. These bio-based solvents are derived from agricultural crops rich in carbohydrates, such as corn, wheat and beets, or from esters of lactic acid and natural acids. Provided below are solvents from AstroBio, with the solvents that they replace given in brackets:

AstroBioTM VG (Naphtha), AstroBioTM BC (Butyl glycol), AstroBioTM SD8 (d-limonene), AstroBioTM K1(Acetone), AstroBioTM K3 (Methyl isobutyl ketone (MIBK)), AstroBioTM DP (DPM (Dipropylene glycol monomethyl ether)), AstroBioTM BA (Butyl acetate), AstroBioTM TL2 (Methoxypropanol), AstroBioTM XT (Toluene , xylene), AstroBioTM NS, NS3 (NMP & NEP), AstroBioTM VL (Benzyl alcohol), AstroBioTM PA ((1-Methoxy-2-propyl) acetate), AstroBioTM SR (Paraffins D60), AstroBioTM S100 (Paraffins D100), AstroBioTM AP (NMP (N Methyl-2-pyrrolidone)).

These solvents have their application in degreasing, cosmetics, leather, composites, paint, release agents, coil coatings, cookware, machinery cleaning and lubricants.[30]

Vertec BioSolvents:

Vertec BioSolvents Inc. is based in the US and provides environmentally friendly alternatives to traditional petroleum-based solvents. Its products are primarily derived from corn, soybeans, citrus fruits and other renewable feedstocks. Vertec BioSolvents has seven issued patents in solvent blends and applications. Some of the bio-based solvents are VertecBioTM EL, VertecBioTM ELSOL®, VertecBio Gold® (US6096699A, US6191087B1, EP0944575B1), VertecBioTM Citrus (US6797684B2), VertecBioTM DLR, VertecBioTM 5516, VertecBioTM Ethyl acetate, VertecBioTM EL Pine, VertecBioTM Ink Zapper (US6284720B1), VertecBioTM Sanitisation. These solvents replace a wide number of petroleum-based solvents. They find application in agriculture, ink formulations, paint & coatings, petroleum and industrial manufacturing.[31]

Bioeutectics: A start-up founded in 2021, Bioeutectics is revolutionalizing the solvent industry, turning it into a natural, biodegradable and sustainable one. Aligned with customers’ needs, it customizes safe and natural solvents for every industrial process. . Bioeutectics has a great impact on food, pharma and personal care industries.It is one of the 10 Cleantech finalists in LATAM and the Caribbean.[32]

Conclusion:

The bio-based solvent market is expected to surge in the near future and remain as a niche market for quite sometime, as all the industries are inclined towards sustainability. The EU also declared that the bio-based products sector would be a high-priority area with potential for future growth and reindustrialization, while addressing societal challenges at the same time. Consumers’ interest in sustainability is increasing day by day; and as a result, demand for renewable solvents is exponentially increasing. Research on new solvents and new bio resources is also expected to continue. Partnerships and collaborations to manufacture and commercialize bio-based solvents are expected to increase exponentially in the near future.

REFERENCE

  1. Volatile organic compounds (VOCs)
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  2. Bio-Solvents: Synthesis, Industrial Production and Applications
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  3. Green and Sustainable Solvents in Chemical Processes
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  4. Green and Bio-Based Solvents
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  5. Bio-Solvents: Synthesis, Industrial Production and Applications
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  6. World’s first car to be fuelled by whisky residue biofuel takes its inaugural journey
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  7. Caledon Green Facility
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  8. Partnership Caldic and Celtic Renewables
    Source
  9. Cargill and HELM partner to build $300M commercial-scale
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  10. Bio-available Solvent Cyrene: Synthesis, Derivatization, and Applications
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  11. Press Release: Circa Group’s Biosolvent Cyrene® Wins ‘Bio-Based Chemical Innovation of the Year’
    Source
  12. Sustainable recycling of cathode scraps via Cyrene-based separation
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  13. Cyrene™ as an Alternative Sustainable Solvent for the Preparation of Poly(lactic-co-glycolic acid) Nanoparticles
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  14. Cyrene™ is a green alternative to DMSO as a solvent for antibacterial drug discovery against ESKAPE pathogens
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  15. Dihydrolevoglucosenone (Cyrene™) as a bio-renewable solvent for Cu(0)wire-mediated reversible deactivation radical polymerization (RDRP) without external deoxygenation
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  16. Cyrene as a bio-based solvent for HATU mediated amide coupling
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  17. Circa And Valmet Partner To Industrialise Biochemicals Production
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  18. SoyGold® Soy Methyl Esters
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  19. Agri-Pure™ Biosolvent
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  20. Agri-Pure™ ChemPoint and Cargill partnership
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  21. Ground-breaking bio-based dry cleaning solvent to be produced by Green Biologics and Kreussler Chemicals
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  22. Systematically in a successful future.
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  23. Braskem and Dutch-based NXTLEVVEL Biochem form collaboration to study the renewable solvents market
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  24. The European Union boosts innovation in the plant protein and oil sectors with support for EcoXtract® from Horizon
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  25. About the eco Extraction
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  26. Ecoxtract Earns Usda Certified Biobased Product Label
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  27. Company news Labelled Solutions.
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  28. ACS Research Article Dry and Aqueous 2MeOx as green solvents for simultaneous production of soybean oil and defatted meal
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  29. 2-Methyloxolane as a Bio-Based Solvent for Green Extraction of Aromas from Hops ( Humulus lupulus)
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  30. Products Line
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  31. BioSolvents Product
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  32. Bioeutectics
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Disclaimer:

  • This document has been created for educational and instructional purposes only
  • Copyrighted materials used have been specifically acknowledged
  • We claim the right of fair use as ascertained by the author

Posted Date: July, 2022

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