Croda’s renewable ethoxylates add another string to ethanol’s bow

Posted in: biobased

22/06/2017
Ethanol is already established as a biofuel, but when converted into ethylene can have a huge role to play in biobased chemicals.

Ethanol, widely known as a biofuel, has a growing presence in the chemical industry. In itself, ethanol is a low volume speciality chemical with various uses as a solvent, but with a single chemical transformation it is readily transformed to ethylene, the largest volume chemical intermediate in the world.

Passing ethanol over an alumina or zeolite catalyst produces high purity ethylene in high yields, allowing the production of derivatives including high and low density polyethylenes, PVC, PET and ethoxylates. The ethylene value chain represents an annual production volume of over 130 million tonnes and a global market forecast to be valued at almost $250billion by the end of the decade.

Traditionally produced from petrochemical naphtha, the biggest consumers of ethylene are the polyethlyenes (high density, low density and linear low density). They are also the largest consumers of biobased ethylene. The Brazilian chemical giant Braskem has been producing biobased polyethylene from sugarcane-derived ethanol since 2007. In 2010, Braskem inaugurated its 200,000tons per year biobased ethylene plant in Triunfo, Rio Grande do Sul. The Braskem product line, marketed under the ‘I’m Green™’ brand, includes high-density, low-density and linear-low-density polyethylene, for rigid packaging applications, films, caps and closures, and bags. Braskem’s biobased polyethylene has been used as a 3D printer filament aboard the international space station, with the first printed item being a pipe connector for a vegetable irrigation system.

Braskem also uses ethanol in the production of Ethyl Tertiary-Butyl Ether (ETBE), and has developed an ethylene based metathesis route to polypropylene (which they have yet to commercialise).

Ethanol is the key intermediate in the production of biobased polyethylene terephthalate (PET) plastic. PET is produced from monoethylene glycol (MEG) and terephthalic acid: dehydration of ethanol to ethylene is followed by conversion to ethylene oxide, and finally MEG. This process provides a route to PET with a 30% biobased content. The PET market is not only large - over 70million tons of PET is used as plastic resin and textile filament - but is also a consumer touch point for the biobased chemicals industry. Plastic bottles are commonly produced from PET and with iconic brands such as Coca Cola, Heinz and Pepsi looking for new opportunities to demonstrate their sustainable credentials the potential for biobased PET has not been overlooked. Under the PlantBottle® brand Coca Cola have distributed over 35 billion packages and have the ambition to convert all new PET plastic bottles, to PlantBottle packaging (up to 30% plant-based) by 2020.

In 2012, Coca-Cola, Ford, H.J. Heinz, NIKE and Procter & Gamble announced the formation of the Plant PET Technology Collaborative (PTC), a strategic working group focused on accelerating the development and use of 100% plant-based PET materials and fibre in their products. There are numerous companies - including the chemical giants BASF - who have formed a joint venture with Dutch technology developer Avantium, working towards the production of 100% biobased PET or its analogue PEF. Commercial production could be realised by 2020.

Ethylene oxide also has important derivatives beyond monoethylene glycol. It is used to produce ethoxylates, chemicals with a wide range of applications in many sectors, including cleaning products, cosmetics, and paints. Although many ethoxylates are partially biobased, being produced from fatty acids, the lack of access to biobased ethylene oxide has prevented the sale of 100% biobased ethoxylates.

Thanks to the UK speciality chemical ingredients company Croda, the situation is now changing.

Croda is a company rooted in the production of high performance chemicals from renewable resources. Founded in 1925, the company’s first product was lanolin, the refined form of wool grease, a product still widely used today across health, personal and industrial sectors. Over the subsequent nine decades Croda has grown into a £1billion business.​

 

For Croda, the high performance of their ingredients is paramount and goes hand in hand with their longstanding commitment to investing in sustainability and putting innovation into action. This commitment and drive has resulted in the company having an impressive 70% of its raw materials derived from renewable sources.

In 2015, Croda began work on a $170million project at its Atlas Point manufacturing site in New Castle, Delaware. Their aim was to produce biobased ethylene oxide as basis for their ethoxylate product range. The project has now come to fruition with the plant successfully up and running, and later in 2017 Croda will release a full range of 100% biobased ethoxylates.

Although “Greener”, non-ethoxylated ingredients, have been used in the development of more natural formulations, many in the industry feel the performance has not yet met the levels of the traditional ethoxylates. According to Croda the 100% Bio-based ECO Range of ingredients will enable its customers to meet their goals of delivering 100% renewable, high-performance products to their consumers and reduce the reliance on fossil fuels. Croda’s Bio-based ECO range will contain more than 60 different ingredients, making it the widest range in the industry. Additionally, Croda will also produce a non-ECO branded range of products, not attaining 100% biobased content, but having a highly improved biobased profile over traditional versions.

Croda is a participant in the USDA’s BioPreferred program, and through the program are supporting the uptake of biobased products. Many of Croda’s products are among the 2,500 products, in 100 different product categories, certified by the program and the ECO range is expected to join this list. Their achievements have been recognised by their receiving the award for “Most Innovative Use of Green Chemistry” from the New York Society of Cosmetic Chemists for their biobased ethoxylate development.

The next addition to ethanol derivatives family is likely to be ethyl acetate. Through its subsidiary Prairie Catalytic, the renewable che

micals company Greenyug is targeting the $4 Billion ethyl acetate market. The Prairie Catalytic production facility will be located next to Archer Daniels Midland Company's (ADM) Corn Processing Plant in Columbus, Nebraska, with ADM supplying the project with bioethanol feedstock and other services. Construction of the 50,000ton facility is anticipated to start during 2017 with production set to begin in 2018.

Without doubt the political drive to develop biofuels such as ethanol has created an industrial base from which the biobased chemical industry can grow. As with the petrochemical industry, fuel may create the volume but chemicals offer the value, and we are likely to see further strings added to ethanol’s bow in the future. However, these chemical projects remain large scale investments and are not without risk, with this in mind and staying with the archery theme we should complement companies like Croda and allow them the honour of wearing the proverbial feather in their cap.

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This article was written by Dr Adrian Higson, Lead Consultant for Biobased Products at NNFCC, and Bob Horton, Research Analyst at NNFCC.

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