Levulinic acid biorefineries

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Publication date: 16/11/2015
Last update: 20/02/2016

Description 1,2

Levulinic acid (also known as 4-oxopentanoic acid or γ-ketovaleric acid) is an organic compound with chemical formula C5H8O3. It is a white crystalline solid soluble in water and polar organic solvents. It contains ketone and a carboxylic group whose presence results in interesting reactivity patterns. It is one of the more recognized Biobased Chemical Building Blocks, a starting material for a wide number of compounds (see Applications below). In fact, it was recognized by the US DoE as one of the top biobased platform chemicals of the future and it can successfully address many performance-related issues attributed to petroleum-based chemicals and materials.

Process technologies 1,3,4,5

The controlled degradation of C6-sugars by acids is the most widely used approach to prepare levulinic acid from lignocellulosic biomass. Other methods have also been studied, for instance, the hydrolysis of acetyl succinate ester, the acid hydrolysis of furfuryl alcohol and the oxidation of ketones. However, these methods require expensive raw materials and result in relatively high amounts of by-products.

Acidic hydrolysis of lignocellulose (a simple thermochemical process) causes the breakdown of polymer sugars to both C5 and C6 sugars. A degradation product of C6 sugar is 5-hydroxymethylfurfural (HMF), a furan compound that can be converted (via hydration) to levulinic acid and formic acid in equimolar amounts. Dehydration of C5 sugars (hemicellulose fraction) results in furfural, which can be delivered as a product or upgraded to levulinic acid. Lignin along with some degraded cellulose and hemicellulose and any inerts, comes out of the process as a carbon-rich char mixture. Many concepts for the commercial production of levulinic acid are based on this strong acid technology. Companies who developed process based on this model are: Biofine, DSM, GFBiochemicals and Segetis (acquired by the previous one).

Figure 1. Continuous production of levulinic acid by the Biofine Technolgy (extracted from Reference 1)

Applications 6,7,8

Levulinic acid can serve as an incredibly versatile building block for chemicals and materials derived directly from biomass. It is used as a precursor for:
  • Fuel additives. Levulinate esters are additives for gasoline and diesel transportation fuels. For instance, they can replace current cetane improvers and cold-flow performers for diesel. They may also replace lubricity improvers. Methyltetrahydrofuran (MeTHF), a levulinic acid derivative, can also be blended up to 50% with gasoline to increase vehicle performance and reduce air emissions.
  • Solvents. Levulinic acid esters, gammavalerolactone (GVL) and MeTHF are suitable solvents for a number of applications. GVL can replace ethyl acetate and MeTHF can be used as a substitute of tetrahydrofuran (THF) in the fine chemical and pharmaceutical industry.
  • Polymers and plasticizers. Levulinic acid-derived ketal esters can replace major phthalate-based plasticizers. Methyl butanediol (MeBDO) has potential as a monomer for polyurethanes. GVL can be a monomer for polyester-polymers and starting materials for pyrrolidinone-isomers.
  • Resins and coatings. Levulinic acid can be used in polyester resins and polyester polyols to increase scratch resistance for interior and exterior coatings. Its derivative Diphenolic Acid (DPA) is used in protective and decorative finishes.
  • Agro-chemicals. Its derivative delta-amino levulinic acid (DALA) is used as an herbicide on lawns and certain grain crops.
  • Pharmaceuticals. Levulinic acid is used in anti-inflammatory medication, anti-allergy agents, mineral supplements and transdermal patches. DALA is used for diagnosis and treatment of cancer.
  • Personal care. Levulinic acid and its derivatives are used in organic and natural cosmetic compositions for antimicrobial, perfuming, skin conditioning and pH-regulating purposes.
  • Flavors and fragrances. Levulinic acid esters are often used as niche fruity flavor and fragrance ingredients.

Figure 2. Levulinic acid as platform chemical (extracted from Reference 8)

Commercial plants - Operational 9,10

Caserta Biorefinery
Owner
GFBiochemicals  (www.gfbiochemicals.com)
Location
Caserta (Italy)
Feedstocks
Cellulosic feedstock.
Technology
Proprietary technology platform. Thermochemical conversion: acidic hydrolysis of lignocellulose. Recovery and purification of levulinic acid. Formic acid and char are recovered.
Capacity
10,000 tons per year (scale up to full capacity by 2017).
Start-up
July 2015.

Note
It does exist an unorganized market in China. It was not possible to find information about the plants of the suppliers: Hebei Langfang Triple Well Chemicals, Hebei Shijiazhuang Worldwide Furfural & Furfuryl Alcohol Funan Resin, Jiangsu Yancheng China Flavor Chemicals, Shijiazhuang Pharmaceutical Group Ouyi Pharmaceutical, Shanghai Apple Flavor & Fragrance and Shandong Zibo Shuangyu Chemical.

Commercial plants – Under construction or planning 11
Location
Companies
Capacity
Status
To be determined
Segetis (www.segetis.bio).
JavelinTM technology.
Note: Segetis has been acquired by GFBiochemicals.
15 ktons/y
Planned for 2017.

Pilot and demonstration plants 3,11

Location
Companies
Capacity
Status
Golden Valley (MN, USA)
Segetis (www.segetis.bio).
Note: Segetis has been acquired by GFBiochemicals.
-
Demonstration plant. Fully operational since 2012.
Gorham (ME, USA)
Biofine Technology (www.biofinetechnology.com)
-
Demonstration plant. Operational since 2014.
Limerick (Ireland)
DIBANET Project (www.dibanet.org).
6 kg/h of biomass (processed)
Pilot plant. No longer operational.
San Fernando de Henares (Madrid, Spain)
LIFE + WALEVA project (www.waleva.eu).
Partnerchip: Técnicas Reunidas, CICYTEX and FEIQUE.
1 ton/month of dry rice straw (processed).
Pilot plant. Expected to be operational by Q4 2016.

_________________________________________________________________________________
REFERENCES
1 B. Girisuta: “Levulinic Acid from Lignocellulosic Biomass”. PhD Thesis. November 2007.
2 T. Werpy, G.R. Petersen: “Top Value Added Chemicals from Biomass. Volume 1: Results of Screening for Potential Candidates from Sugar and Systhesis Gas”. US DoE, August 2004.
3 http://www.biofinetechnology.com.
4 “Bio-Based Chemicals: Value Added Products from Biorefineries”. IEA Bioenergy, Task 42 Biorefinery.
5  P. Harmsen, M. Hackmann: “Green Building Blocks for Biobased Plastics”. Wageningen UR Food & Biobased Research, March 2013.
6 http://www.gfbiochemicals.com/products/.
7 http://www.segetis.com/markets/.
8 http://biofinetechnology.com/wp-content/uploads/2014/02/Presentation-for-Canadian-Forest-Products-Association-Toronto-February-2014.pdf.
9 http://www.gfbiochemicals.com/technology/.
10 http://www.radiantinsights.com/research/levulinic-acid-market-analysis-and-segment-forecasts-to-2020.
11 http://www.segetis.bio/technology/#javelin.

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