The Sexy 7: The bio markets and apps in PET, PX, PEF, PLA, PHA, PBS, and PE

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200,200 downloads for the DOE’s classic report on value-added chemicals — but some hot molecules are missing!

Top Value Added Chemicals from Biomass” a 2004 survey, completed by staff led by Gene Petersen and Todd Werpy, at the Pacific Northwest National Laboratory and NREL, is the Dark Side of the Moon of biobased, a perennial classic that has recorded 201,200 downloads to date via the Digest’s SuperData, alone, and gives the down-low on why 12 bio-based chemicals matter more than others.

Any number on entrepreneurs started down the road to developing companies and technologies to make each of the Big 12 — and some of them, like glucaric and succinic acid, have gone on to commercial-scale success.

Yet, there are 7 Monster Molecules that never made the list, 7 P’s in a Pod — PET, PX, PEF, PLA, PHA, PBS, and PE. Some of them have become even more important than any of those on the TVAC list — they are Billboard-esque Hot Bullets in their own right.

Bullish or super-bullish?

Everyone agrees that biobased chemicals are on a fast rise, but how fast is a question.

nova institut reports that production capacity for bio-based polymers grew by 4% to 6.6 Million tonnes from 2015 to 2016. This represents a share of 2% of the global polymer market. The bio-based polymer turnover was about €13 billion worldwide in 2016 compared to €11 billion in 2014. Production capacity of bio-based polymers is forecasted to increase from 6.6 million tonnes in 2016 to 8.5 million tonnes by 2021.

The development of the bio-based polymer market aligns to the overall growth rate of the polymer market as a whole. In contrast to a 10% annual growth between 2012 and 2014, the capacity growth data now show a 4% annual growth rate from 2015 to 2021. This is almost the same as for the overall global polymer capacity. The main reasons for this slower increase in capacity are low oil prices, poor political support and a slower than expected growth of the capacity utilization rate.

More bullish? Future Market Insights predicted in “Bio-plastics Market: Global Industry Analysis and Opportunity Assessment 2014 to 2020”, that the global bio-plastics market is expected to account for $43.8 Bn by 2020, registering a CAGR of 28.8% during the forecast period. A growing beverage packaging industry, government support for adopting bio-based materials, and rising consumer acceptance for bio-plastics are expected to contribute to the growth of the global bio-plastic market over the forecast period.

The rock star?

The bio-PET material segment dominates the bio-plastics market, and was estimated to be US$ 5.6 Bn in 2014. This segment is expected to reach $ 29.1B by 2020, with a momentous CAGR of 31.4% for the forecast period. Moreover, an increasing demand for bio-plastics from the beverage packaging industry and effectiveness of bio-plastics in one-time use application has driven the demand for the bio-PET in the last few years.

Global bioplastics market to grow at 28.8% rate through 2020: Report

Either way, there’s growth, and let’s look at those molecules and their progress and prospects.

PET

Clear plastic bottles? That’s PET. The Plant Bottle? That’s 30% bio-based content in PET, courtesy of making MEG (ethylene glycol) from renewables. The other portion is biobased PTA, which is a tougher-to-make.

A recent report from Global Market Insights concluded that the BIO-PET market size was 496.0 kilo tons in 2015, as per the latest research report by Global Market Insights, Inc. Growing concerns towards GHG emissions coupled with bioplastics emergence as an alternative in packaging and automotive industry may stimulate global bio based PET market size.

The global market for PET is about 50 million tpa ($30 billion) and growing at 6% CAGR. GMI said that global biobased PET market size may generate $13.1 billion by 2023. Increasing importance of sustainable packaging, especially in China and India, may positively influence bio based polyethylene market size growth. Key Industry participants, The Coca-Cola Company and Toray, have formed strategic partnerships with bio based product manufacturers such as Gevo and Virent, for the development 100% bio PET.

Report says global biobased PET market size may reach $13.1 billion by 2023

There are two big alliances.

The Coca-Cola development team includes Gevo, Virent, and Avantium, who are each developing a different technology to produce pX.  Gevo aims to produce pX from isobutanol via fermentation. Virent’s process hydrogenates and condenses sugars in a high pressure aqueous process called BioForming to produce oxygenates that are catalytically converted to a mixture including pX.  Paraxylene from Virent was used to produce Coca-Cola’s first 100% bio-based PET bottles.  Avantium is exploring routes to pX involving a multi-step reaction of furan derivatives and olefins.

Another alliance working to develop and commercialize bio-based aromatics is Anellotech and partners  Japanese beverage giant Suntory, French process developer IFPEN, licensing and engineering firm AXENS, and catalyst provider Johnson Matthey. A 25-meter tall development and testing plant is under construction in Texas. The Anellotech one reactor process – Bio-TCat™ (one step from biomass to aromatics including pX) provides significant capital and operating cost savings compared to the multi-step processes.

It all will come down to the key molecules that everyone in the space is chasing. One path is through making renewable paraxylene (an ingredient in PET). The other is to replace PET with PEF and make the latter renewably.

Let’s look at those now.

PX

Para-xylene (pX), currently produced by the catalytic reforming of naphtha, contributes 80% of the carbon in PET. There are three players to watch right now — Anellotech, Gevo and Virent. Others will come along.

On the Virent front, Tesoro has acquired Virent. The acquisition, the partners said, will support the scale up and commercialization of Virent’s BioForming technology for the production of low carbon bio-based fuels and chemicals. As a result of the acquisition, Virent will become a wholly owned subsidiary of Tesoro and remain in Madison, Wisconsin.

In late 2015, Virent was named the #1 Hottest Small Company in the Advanced Bioeconomy by the readers and invited selectors in the Digest’s Hot 40. The companies initiated a strategic relationship in January 2016, and have worked together to establish a forward plan to scale-up the technology and reduce deployment risks to meet the increasing demands for high quality, renewable fuels and chemicals.

Tesoro to Acquire Virent 

On the Anellotech front, Anellotech and IFPEN/Axens engineers completed a successful continuous performance test of the TCat-8 pilot plant as part of unit commissioning in Silsbee, Texas. The test involved continuous injection of MinFree woody biomass feedstock and production of BTX and other valuable chemical by-products.

Additional tests are planned to complete the commissioning phase and then commence process development studies to acquire data for commercial scale-up and design of the process.

The technology is scheduled to open at commercial scale in 2019. Clock is ticking, exciting stuff.

Anellotech Confidential: Pilot running, new mystery investor as catpyro begins to scale

PEF

PEF is a new rival to PET. It’s new and not yet made at world-scale, but tests have shown that it has better barrier properties and can support smaller bottles. For PEF, think FDCA. In that space, think DuPont, and just about anyone who can make 5-HMF, including AVA.

The big news this year was Avantium completing its highly-anticipated initial public offering, raising $109.5M (€103M) via the sale of 9,401,793 shares at $11.70 (€11) per share, giving the company a market capitalization reaches of $294M (€277M). Trading will begin on March 15th 2017 on Euronext Amsterdam and Euronext Bruxelles under the symbol AVTX.

It’s all about going to scale. The Company anticipates to use €65-75 million of the net proceeds of the Offering for the funding of the Joint Venture, enabling it to construct and operate the reference plant for the commercialization of the YXY technology. The company’s first world-scale plant is a 50,000 tons per year FDCA production unit planned for Antwerp as part of a joint venture with BASF. The rest of the funds will be used to build pilot plants for the company’s Zambezi and Mekong renewable chemicals projects, as well general corporate purposes.

Avantium completes “oversubscribed” €103M IPO: heads for first commercial

PLA

Now, let’s look at plastics used in other areas of packaging, besides bottling. Think PLA (polylactic acid) and PHA, which is a bio-degradable alternative.

Sales of biopolymers and resins are predicted to grow to over $5 billion by 2021.   Biomass derived materials have been used neat and as components in composites and blends for the last decade. Products made with high contents of cellulose, starch, proteins, chitosan are common. New products made with biosynthetic products like polylactic acid (PLA) and polyhydoxylalkanotes (PHA) appear on regular basis in the press and on the shelf.       These products include beverage bottles, wood replacements, food packaging, 3D printing, grocery bags and many other applications. New formulations and additives that improve the properties of the biopolymers are being considered.

New Bio Plastics and Resins

Market size? Research and Markets announced the addition of the “Polylactic Acid (PLA) – A Global Market Watch, 2011 – 2016” to their offering. It predicts that the global polylactic acid market is expected to reach US$2.6 billion by 2016 at a CAGR of 28%, globally.

Region-wise analysis shows that Asia-Pacific is forecasted to record the highest growth rate of 29.3% during the analysis period 2011-2016. Europe follows Asia-Pacific with a CAGR of 28.9%. The two Americas are forecast to drive the global market with a CAGR of 27.3%. Volume based studies reveal that the maximum share of growth rate is expected from Asia-Pacific region.

Global polylactic acid market predicted to hit US$2.6 billion by 2016

PLA’s big players include the Total-BASF JV, and Cargill’s NatureWorks (the latter has developed a host of applications under the Ingeo brand).

NatureWorks licenses Metabolix technology for bio-based polylactic acid-based blends

One interesting development to watch. We reported in January that Global Green Chemical has joined with Kaset Thai International Sugar to jointly develop a feasibility study for a biorefinery using sugarcane in Nakhon Sawan province that will produce Lactic Acid and Polylactic Acid from ethanol to feed into the bioplastics market. The investment plan should be ready by year’s end, with the mill and distillery expected to take up to three years to build. Funding for the project will partially come from the company’s IPO set for the second quarter of this year.

Thai companies team up to develop biorefineries to serve the bioplastics industry

PHA

The big story here is Newlight Technologies and it’s AirCarbon

In late 2015, we reported that Newlight Technologies signed a 20-year take-or-pay off-take agreement with Vinmar International for 1 billion pounds of AirCarbon PHA. Critical to the deal? Newlight’s catalyst aims to transform the economics of PHA-based plastics, solving low yields and high cost issues that have kept PHA from competing strongly with petroleum-based plastics.

What is AirCarbon, and what does it do?  Newlight’s 9X biocatalyst generates a polymer conversion yield that is over nine times higher than previous–from a yield ratio of 1:1 to 1:9, enabled by developing a new kind of biocatalyst over 10 years of research that does not exhibit a negative feedback response–fundamentally shifting the cost structure of the greenhouse gas to plastic conversion process, and enabling AirCarbon to out-compete oil-based plastics, such as polypropylene and polyethylene, on price.

Newlight’s biocatalyst works by combining air with methane, and assembling the carbon, hydrogen, and oxygen molecules therein into a long chain PHA-based thermoplastic material.

The Vinmar contract provides for the sale of 100% of AirCarbon PHA from Newlight’s planned 50 million pound per year production facility for 20 years.  The contract will also cover 100% of the output from a 300 million pound per year AirCarbon production facility and a 600 million pound per year AirCarbon production facility for a total of up to 19 billion pounds over 20 years.

One billion pounds of carbon-negative plastic, made from greenhouse gas and pure air

PBS

PBS? It’s polybutylene succinate, so think succinic.

It’s found in everything from boxes, bags, tableware, even mulching films. We want it to be durable and tough — but then we don’t want to last 10,000 years in landfill, either. PBS is in critical ways the Lone Ranger of thermoplastics. Tough enough to get the job done, stays while you need him, but leaves town with a “hi-yo, Silver, and away!”  Or should that be “bio, Silver”?

Most interesting news in the space was the announce last May from Reverdia and Wageningen UR Food & Biobased Research that the partners had launched a joint development program on bio-based PBS compounds for injection moulding. The new bio-PBS compounds will be durable and based on Reverdia’s Biosuccinium.

Good news, kemosabe: Reverdia and Wageningen UR launch development of new Bio-PBS compounds

But keep an eye on BioAmber. We reported in February 2016 that Mitsui had invested an additional C$25 million in the BioAmber joint venture for 10% of the equity, increasing its stake from 30% to 40%. Mitsui will also play a stronger role in the commercialization of bio-succinic acid produced in Sarnia, providing dedicated resources alongside BioAmber’s commercial team. BioAmber will maintain a 60% controlling stake in the joint venture.

Why is that news for PBS? When BioAmber raised $45 million dollars in a 2011 Series B financing , it was avowedly to accelerate the commercialization not only succinic acid but also modified PBS and the round Mitsui & Co’s first appearance as a BioAmber investor. The two eventually partnered to build and operate the previously announced manufacturing facility in Sarnia, Ontario, Canada. The initial phase of the facility is expected to have production capacity of 17,000 metric tons of biosuccinic acid and commence commercial production in 2013.

Mitsui invests $25M in BioAmber JV; raises stake, will “play a stronger role”

PE

Polyethylene? It’s going to be all about apps that are adopted by customers in part because of their renewable attributes. Otherwise, ethylene is going to made at scale using fossil resources and traditional process.

The good news? Polyethylene has flexibility, chemical resistance and recyclability. Just a short step from ethanol, so there’s been long-standing interest from Brazil because it can be made from a renewable resource.

Most fascinating for us, we reported in December on a partnership between Braskem, NASA and MadeInSpace has developed a technology “hat is critical to future manned missions including Mars exploration” – and we are doing this with a bioplastic, Braskem “I’m green” polyethylene.

In summary, the bioplastic is currently in use in the International Space Station where a zero-gravity 3D printer uses it to produce tools and components. For over a year, Braskem’s Innovation & Technology team has been working with Made In Space to develop a Green Plastic solution especially for 3D printing in zero gravity. The partnership will enable astronauts to receive by e-mail digital designs of the parts and then print them, which means dramatic savings in terms of time and costs.

There are great expectations surrounding the project’s benefits, since 3D printing in space was defined by NASA as one of the advances essential for a future mission to Mars .

Voyage to Mars: Braskem, NASA, MadeinSpace launch “3D printing in space” using renewables

But back on Earth, there are some apps coming to market well worth a shout-out. In February, we reported that SYNLawn introduced a new biobased and environmentally renewable polyethylene (PE) product made from Brazilian sugar cane that is sustainably grown under some of the strictest environmental, social, and industrial practices in the world. SYNRenew synthetic turf combines soy-based polyurethane BioCel and EnviroLo backing technology with polyethylene fibers made from sugarcane technology to produce a new and completely biobased synthetic turf product.

SYNLawn producing biobased PE synthetic turf

Beyond the Sexy 7

Let’s look at three cool molecules that didn’t quite make the Sexy 7. Biggest among them is biobased polyurethane, or PUR.

PUR

Lorenz Bauer wrote in the Digest recently

Polyurethanes were invented by Otto Bayer in the 1930s. They are formed by reacting a polyol (a compound with more than two reactive hydroxyl groups per molecule) with a diisocyanate or a polymeric isocyanate in the presence of suitable catalysts and additives. Because a variety of diisocyanates and a wide range of polyols can be used to produce polyurethane, a broad spectrum of materials can be produced to meet the needs of specific applications. They are used in products ranging from coatings and adhesives to shoe soles, mattresses and foam insulation. Global demand for polyurethane products approximated 20 million tons in 2014.    Total revenues from the market are expected to reach $54.2 billion by 2019.   The renewable polyols have been available for about a decade, and market for these and other renewable polyurethanes is anticipated to grow to $10.3 billion in 2023.

Clearly, the major drivers for moving to biomass derived materials has to be their low cost and performance; although government regulation and consumer preference are playing an increasing role for some applications like automobile interiors and footwear.

Sustainable polyurethanes are a fast growing segment of the polymer market and represent a success story for the investment by government and industry in products with a lower carbon footprint. They are the result of 100s of millions of dollars of research and development efforts. Their success is clearly tied to their lower costs and equivalent or better performance compared to petroleum derived products. This makes them attractive even without the bonus of being able to be marketed as a “green” alternative.

The wide variety of polyurethane applications provides many appropriate size niche markets for introduction of new products.  It is possible for modest size first generation plants to provide sufficient product to be considered a trusted supplier by end users.

Polyols can be made from a number of biomass derived materials including natural oils like: castor, palm and soy oil; and sugars like: adipic and succinic acids, and even captured waste CO2.   Materials with a performance rivaling or exceeding petroleum-based products are available  Sustainable polyols are currently capable of replacing 33-55% of the petrochemical in polyurethanes.   Several companies are blending the natural oils with recycled materials to produce materials with significantly higher “green” carbon contents. Substituting biomass derived cyanates allows the production of 100% renewable polymers.

Sustainable Polyurethanes and the Bio Economy

Others to watch. What about PIP and PMMA?

As E4Tech related in this report:

There are 33 products of particular interest, given the level of industry activity, and as highlighted by US DOE’s “Top10” biochemicals and IEA Bioenergy Task 42 reports – the majority are primary products (first step after sugars), with some key intermediates added (e.g. ethylene.”), and E4tech added 8 additional downstream bio-based polymer pathways (PLA, PET, PBS, PEF, PE, PMMA, and PIP).

The Materials Superhighway

The Bottom Line

The DOE had its Top 12, but we like the Sexy 7 for having more immediate commercial application. They all make good bio-based options, but the new 10 are proving to have greater near-term market appeal.

What’s especially interesting to us is the transition from venture-backed companies chasing the original 12, to the strategic-backed entries chasing the Sexy 7. Braskem, DuPont, Cargill, Vinmar, BASF, Mitsui, Corbion, Purac, DSM – just some of the players working on this group — that’s hard evidence from established players that for these bio-based molecules , the time has come.