Renewable Solvents

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

Bio-BDO^TM (1, 4 butane Diol)

Genomatica created Bio-BDO^TM (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-BDO^TM 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.

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 The reactor is maintained at a temperature between 250 and 450°C, and gaseous products and char are withdrawn from the pyrolysis reactor.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.

Cyrene 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.

Recently, 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:

SOLVONK4^TM
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.

Green Biologics used their patented fermentation (US20150368678A1) process, using the Clostridium saccharoperbutylacetonicum microorganism to convert feedstocks into the bio-based n-butanol. SOLVONK4^TM 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]

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]

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.

AstroBio^TM 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:

AstroBio^TM VG (Naphtha), AstroBio^TM BC (Butyl glycol), AstroBio^TM SD8 (d-limonene), AstroBio^TM K1(Acetone), AstroBio^TM K3 (Methyl isobutyl ketone (MIBK)), AstroBio^TM DP (DPM (Dipropylene glycol monomethyl ether)), AstroBio^TM BA (Butyl acetate), AstroBio^TM TL2 (Methoxypropanol), AstroBio^TM XT (Toluene , xylene), AstroBio^TM NS, NS3 (NMP & NEP), AstroBio^TM VL (Benzyl alcohol), AstroBio^TM PA ((1-Methoxy-2-propyl) acetate), AstroBio^TM SR (Paraffins D60), AstroBio^TM S100 (Paraffins D100), AstroBio^TM 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 VertecBio^TM EL, VertecBio^TM ELSOL®, VertecBio Gold® (US6096699A, US6191087B1, EP0944575B1), VertecBio^TM Citrus (US6797684B2), VertecBio^TM DLR, VertecBio^TM 5516, VertecBio^TM Ethyl acetate, VertecBio^TM EL Pine, VertecBio^TM Ink Zapper (US6284720B1), VertecBio^TM 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.

[1] https://www.pca.state.mn.us/air/volatile-organic-compounds-vocs

[2] https://www.intechopen.com/chapters/69882

[3] https://pubs.acs.org/doi/10.1021/acs.chemrev.7b00571

[4] https://pubmed.ncbi.nlm.nih.gov/29691726/

[5]https://www.researchgate.net/publication/338116860_BioSolvents_Synthesis_Industrial_Production_and_Applications

[6] https://www.celtic-renewables.com/worlds-first-car-to-be-fuelled-by-whisky-residue-biofuel-takes-its-inaugural-journey/

[7] https://www.celtic-renewables.com/production-facility/

[8] https://www.caldic.com/en/news/caldic-and-celtic-renewables-enter-strategic-partnership-to-bring-innovative-bio-solvents

[9] https://www.cargill.com/2021/cargill-and-helm-partner-to-build-$300m-facility

[10] https://pubmed.ncbi.nlm.nih.gov/30044553/

[11] https://www.sustainabilityconsult.com/news/265-press-release-circa-group-s-biosolvent-cyrene-wins-bio-based-innovation-of-the-year

[12] https://www.osti.gov/servlets/purl/1649102

[13] https://pubmed.ncbi.nlm.nih.gov/33275992/

[14] https://pubs.rsc.org/en/content/articlelanding/2020/md/c9md00341j

[15] https://pubs.rsc.org/en/content/articlelanding/2020/gc/d0gc02184a

[16] https://pubs.rsc.org/en/content/articlelanding/2018/ob/c8ob00653a

[17] https://circa-group.com/news/circa-and-valmet-partner-to-industrialise-biochemicals-production/

[18] https://www.chempoint.com/products/agp/soygold-soy-methyl-esters

[19] https://www.cargill.com/bioindustrial/agri-pure-biosolvent

[20] https://www.chempoint.com/en-emea/news/2022/partnership-annoucement-cargill-agri-pure-partnership

[21] https://www.prnewswire.com/news-releases/ground-breaking-bio-based-dry-cleaning-solvent-to-be-produced-by-green-biologics-and-kreussler-chemicals-300656233.html

[22] https://en.kreussler-chemie.com/customers/textile_cleaners/systemk4.html

[23] https://www.braskem.com.br/news-detail/braskem-and-dutch-based-nxtlevvel-biochem-form-collaboration-to-study-the-renewable-solvents-market

[24] https://ecoxtract.com/wp-content/uploads/2021/05/PR-The-European-Union-boosts-innovation-in-the-plant-protein-and-oil-sectors-with-support-for-EcoXtract%C2%AE-from-Horizon-2020.pdf

[25] https://ecoxtract.com/about-the-eco-extraction/

[26] https://ecoxtract.com/ecoxtract-earns-usda-certified-biobased-product-label/

[27] https://ecoxtract.com/wp-content/uploads/2021/11/Company-news_Labelled_Solutions.-EcoXtract.pdf

[28] https://ecoxtract.com/wp-content/uploads/2021/06/ACS-Research-Article-Dry-and-Aqueous-2MeOx-as-green-solvents-for-simultaneous-production-of-soybean-oil-and-defatted-meal.pdf

[29] https://pubmed.ncbi.nlm.nih.gov/32283752/

[30] https://www.astrobiosolvent.com/product-line/

[31] https://www.vertecbiosolvents.com/products

[32] https://www.bioeutectics.com/