Glucaric acid biorefineries

Publication date: 14/12/2015

Last update: 24/05/2017

Description ^1,2,3,4

D-Glucaric acid, also called saccharic acid, is a chemical compound with formula C₆H₁₀O₈ and member of a large family of molecules known as oxidized sugars. It is a naturally occurring aldaric acid, typically found in small amounts in a variety of fruits and vegetables. It is a highly functionalized compound with four chiral carbons and a plethora of reaction pathways. Its commercial potential was unveiled in the report “Top Value Added Chemicals from Biomass” from the Department of Energy of USA which described its use as a building block for a number of polymers, including new nylons and hyperbranched polyesters.

Process technologies ^{1,3,4,5,6,7,8}

The synthetic preparation of D-glucaric acid dates back to a report of Sohst and Tollens (1888) who carried out the nitric acid oxidation of D-glucose to D-glucaric acid. Current methods for its production are based on this process and involve the chemical oxidation of D-glucose, frequently with nitric acid. Although modest yields of D-glucaric acid are obtained due to competing side reactions generating numerous oxidation products, the method remains attractive for commercialization because of its relative simplicity with nitric acid serving as both solvent and source of the oxidizing agent. In fact, the first commercial plant uses a proprietary technology developed by Rivertop that consists in a one-pot oxidation process without NO_x release (modification of the conventional process).

Alternative oxidization methods have been reported that include catalytic oxidation with oxygen using a platinum catalyst and chlorine and bromine based oxidations employing TEMPO as a catalyst. Catalysts have been shown to increase D-glucaric acid yields, however, such catalysts are generally quite expensive. One of these processes is already being tested in pre-commercial stages: Rennovia and Johnson Matthey Process Technologies are running a mini-plant for the catalytic aerobic oxidation of glucose to glucaric acid.

Figure 1. Derivatives of glucaric acid (extracted from Reference 1)

The possibilities for a cheaper and more environmentally friendly process are concealed in the biological production of D-glucaric acid. Some biological synthetic routes have been proposed. For instance, it can be obtained from D-glucose in recombinant Escherichia coli. Kalion, an early stage industrial biotech company, is working on low-cost access to glucaric acid using this kind of fermentation technology. Further work will be necessary to improve the process in order to scale-up the production from the lab to the commercial environments.

Applications ^9,10

Glucaric acid is an emerging platform chemical with a wide range of applications:

• Intermediate in the production of biobased adipic acid. A world scale plant can consume about 225 kton per year of glucaric acid.
• Phosphate-free detergents and biodegradable cleaners. The salts of sugar acids can be applied to chelate various metal ions. Those detergent builder demonstrates binding capacity to sequester free calcium at a rate comparable to that of phosphates.
• Anti-corrosion additives. Glucaric acid has the capacity to drop pH in operating conditions to levels suitable for various applications in upstream and downstream oil and gas development.
• Cement and concrete additives.
• Adhesives and coatings.
• Food ingredients and animal feed acidulant.
• Therapeutic. Antitumor agent via inhibition of carcinogen-DNA binding and cholesterol-reducing agent.

Biorefineries at commercial scale and pilot plants ^{7,11,12,13,14}

Below, a summary of the main characteristics of the facilities at commercial scale and pilot plants that are operating or under construction at the time of writing.

Commercial-scale facilities - Operating
Owner	Location	Feedstocks	Technology	Capacity	Status
Rivertop Renewables  and DTI.	Danville (Virginia, USA).	Various sugars and sugar alcohols.	Proprietary technology developed by Rivertop - Nitric acid oxidation of D-glucose to D-glucaric acid process without NOx release.	At full capacity the plant is now capable of producing more than 9 million dry pounds of sodium glucarate product per year, an increase of approximately 15% over original design projections.	Construction began in December of 2014 and the first commercial production runs of glucarate-based products started in August of 2015.

Pilot facilities - Operating
Owner	Location	Feedstocks	Technology	Capacity	Status
Johnson Matthey Process Technologies and Rennovia.	Stockton (England).	Glucose.	Catalytic aerobic oxidation of glucose to glucaric acid.	-	In March 2014, the companies announced their collaboration to develop and commercialize production technology for biobased glucaric acid and adipic acid. They successfully started-up a mini-plant for production of glucaric acid in July 2015.

Other movements that could result in the implementation of new facilities:

- February 2017: Johnson Matthey and Rennovia announced that they have signed a license agreement with Archer Daniels Midland Company (ADM) to provide catalyst and process technology for catalytic production of biobased glucaric acid.

- April 2017: Kalion and Lawrence Berkeley National Laboratory have been awarded $200,000 to reach full manufacturing scale production of glucaric acid and glucuronic acid by creating a manufacturing-ready production strain and then scaling to generate an appropriate process.

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REFERENCES

1 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.

2 “Bio-Based Chemicals: Value Added Products from Biorefineries”. IEA Bioenergy, Task 42 Biorefinery.

3 T.N. Smith, K. Hash, C.-L. Davey, H. Mills, H. Williams, D.E. Kiely: “Modifications in the nitric acid oxidation of D-glucose”. Carbohydrate Research, 350 (2012), 6–13.

4 E.C.-J. Shiue: “Improvement of D-Glucaric Acid Production in Escherichia coli”. PhD Thesis, MIT, February 2014.

5 Rivertop – Oxidation Process (accessed on 7th December 2015).

6 G.M. Diamond, V. Murphy, T.R. Boussie (Rennovia, Inc., Menlo Park, California, USA): “Application of High Throughput Experimentation to the Production of Commodity Chemicals from Renewable Feedstocks”. Modern Applications of High Throughput R&D in Heterogeneous Catalysis (Chapter 8), 2014, 288-309.

7 Rennovia press release (July 16, 2015): “Johnson Matthey Process Technologies and Rennovia Announce On Time Start-up of Mini-Plant for Bio-Based Glucaric Acid Production Using Jointly Developed Technology”.

8 Kalion – Portfolio – Glucaric acid (accessed on 10th December 2015).

9 Rivertop – Application Directory (accessed on 7th December 2015).

10 Rennovia – Markets (accessed on 7th December 2015).

11 Rivertop press release (October 6, 2015): “Rivertop Renewables and DTI announce commercial production of glucaric acid”.

12 Rivertop press release (March 29, 2016): “Rivertop Renewables and DTI exceed nameplate capacity of first glucarate production facility”.

13 Rennovia press release (February 21, 2017): “Johnson Matthey and Rennovia Announce License Agreement with ADM for Glucaric Acid Production Technology”.

14 Berkeley Lab press release (April 21, 2017): “Four Small Businesses to Collaborate with Berkeley Lab Through Small Business Vouchers”.