Depth of Processing: Chemistry

Instant Genome Sequencing: Life Technologies New Sequencer

2012-01-21T11:34:00.001-05:00

It can read your DNA in just 24 hours.

It seems like science fiction, but Life Technologies, has a table top sequencing machine for $100,000 to 150,000. It does a whole human genome in a day.

Life Technologies sequencing chip. Note the tubes that deliver
reagents.

The secret is a multi-parallel sequencing device. The press release text is pretty impenetrable, but they say it: "perform[s] direct, real-time measurement of the hydrogen ions produced during DNA replication. A high-density array of wells on the Ion semiconductor chips provides millions of individual reactors, and integrated fluidics allow reagents to flow over the sensor array. This unique combination of fluidics, micromachining, and semiconductor technology enables the direct translation of genetic information (DNA) to digital information (DNA sequence), rapidly generating large quantities of high-quality data." Link

More recently Life Tech's archrival Illumina is suing them for patent enfringement on their analysis chip design.

Just eleven years ago, a collection of the scientists across the world worked to sequence the human genome the first time, and finished in 2003 after thirteen years. Just eight years later, we can do it in an day.

I remember how crazy it seemed when Star Trek NG's Dr Crusher put a few drops of blood in her "tricorder," and this little box sequenced it in a minute. Crazy because that would take a whole lab years, but now, it is not so crazy.

Renmatix Supercritical Water Process for Cellulose Degradation Gains Momentum

2012-01-03T06:34:00.000-05:00

Renamtix, a small King of Prussia Pennsylvania company, is gaining support for its degradation process for wood byproducts into fermentable sugars. The process uses supercritcal water to soften the wood. The company claims the process is patented, but Renmatix has no patents under its name.

BASF invested $30 million in the company, which means their must be something substantive in Renmatix investor pitches. $20 million was contributed by other investors. The biomass-to-sugar proto-industry has contracted lately as new enzymatic process prove difficult to scale up, and syngas routes choke competing with natural gas.

Renmatix approach may show an economic advantage for non-enzymatic routes. Their route also supports the green chemistry principle of not destroying bonds in the feedstock unnecessarily, when they could be used in later step.

Renmatix has a pilot plant that consumes 3000 kg/day of wood fiber, but suspiciously Renmatix does not report how much "industrial sugar" the process can produce per day. What is "industrial sugar" anyway?" I suppose it is an impure sugar mixture sufficient to support yeast or bacterial fermentation, but not clean enough for animal feed.

More on Bio-Succinic Acid

2011-10-20T21:05:00.001-04:00

The news is that BASF and Purac are teaming up for a venture in succinic acid. Interestingly the process will absorb carbon dioxide, so it probably is an attempt to gain greenhouse gas credits as well.

Purac is a big lactic acid producer, and they have been working with BASF for two years.

Succinic acid could be a major building block for C-4 chemicals.

Bio-Succinic Acid

2011-06-26T08:39:00.004-04:00

BioAmber plant in Pomacle France.

BioAmber has a biobased succinic acid plant in France with a capacity of 3,000,000 kg. Succinic acid is used to make polyester resins and as a raw material for further chemical manufacturing. They are planning to build a plant in North America of 20,000,000 kg capacity, probably near Minneapolis. They have plans for Brasil and Asia too.

These plants are making succinic acid with genetically engineered organisms. BioAmber uses an E. coli for fermentation, and has elaborate separation process to produce the pure succinic acid. As mentioned in other posts, the trick when making bio-acids is the separation from the other acids.

BioAmber claims that the process is economical when oil is as cheap as $40/barrel, but that is dubious since the price of fermentable sugar depends on the price of oil.

BioAmber won a 2011 Award from EPA for the technology. BioAmber has agreements with Cargill, DuPont, Mitsubishi Chemical and Mitsui.

Thge company plans to make 1,4 butanediol from succinic acid. Using the diol and the diacid one could make a 100% biosourced polyester which would be desirable for specialty markets.

Bio-Succinic Acid

2011-06-26T08:39:00.000-04:00

BioAmber plant in Pomacle France.

BioAmber has a biobased succinic acid plant in France witha capacity of 3,000,000 kg. Succinic acid is used to make polyester resins and as a raw material for further chemical manufacturing. They are planning to build a plant in North America of 20,000,000 kg capacity, probably near Minneapolis. They have plans for Brasil and Asia too.

These plants are making succinic acid with genetically engineered organisms. BioAmber uses an E. coli for fermentation, and has elaborate separation process to produce the pure succinic acid. As mentioned in other posts, the trick when making bio-acids is the separation from the other acids.

BioAmber claims that the process is economical when oil is as cheap as $40/barrel, but that is dubious since the price of fermentable sugar depends on the price of oi.

BioAmber won a 2011 Award from EPA for the technology. BioAmber has agreements with Cargill, DuPont, Mitsubishi Chemical and Mitsui.

Thge company plans to make 1,4 butanediol from succinic acid. Using the diol and the diacid one could make a 100% biosourced polyester which would be desirable for specialty markets.

BioAcrylic Projects

2011-06-19T20:57:00.002-04:00

The shortages in propylene and acrylic acid have kept BioAcrylic at top of mind. Let's get an update.

3-hydroxy propionic acid is easily
deydrated to make acrylic acid.

In addition to the OPX Biotechnology-Dow project that is at pilot scale, there are multiple industrial projects to make bioacrylics. If you have not heard, OPX Biotechnology is looking to build a $35 million pilot plant for its fermentation based process to acrylic acid via the dehydration of 3-hydroxy propionic acid. Dow is jointly developing this, and OPX says they have a 3-5 year agreement with Dow. [See my previous post on OPX.]

All four projects go through the intermediate 3-hydroxy propionic acid. There are three other bioacylic projects according to OPX's Eggert, Cargill/Novozymes, Nippon Shokubai/Arkema, and Metabolix.

Cargill/Novozymes

The Cargill/Novozymes are licensing the DOE's technology using 3-hydroxypropionic acid, which is made from genetically engineered bacteria.

In bacterial processes, one should not underestimate the cost of separating the 3-hydroxy propionic acid from all the other acids present in a cell.

Novozymes in 2010 saw themselves growing to 18% market share in the US acrylic market, and are "planning" three plants. Truthfully these are pretty vague plans so they may not happen.

Novozymes is claiming 48 hour growth cycles on the bacteria, 95% recovery of the 3-hydroxy propionic acid from the medium, and 98% yield on the dehydration of the hydroxy acid to acrylic acid.

Finally, Novozymes claims that their product is competes with US production with a petroleum price of $65/barrel. With oil at $100, it should be economical. Note that bioacrylics in Brasil is cheaper, and that is because the glycose is cheaper there.

Since acrylic acid can be made from petroleum or from glucose, this technology constitutes a way to tie the two markets together. Novozymes made this graph to show that. This uses acrylic production, but the larger volume ethanol production is the primary tie between the markets.

Nippon Shokubai/Arkema

In 2009, Nippon Shokubai had a lab scale process for dehydration of glycerin to acrolein, and had announced construction of a pilot scale plant. Acrolein is converted to acrylic acid by conventional oxidation, just as convention plants do today. The pilot plant was to cost $2 billion, and be funded by New Energy and Industrial Technology Development Organization or NEDO, and it is majority funded by the Japanese Ministry of Economy, Trade and Industry (METI.) There are no recent press reports on this. Arkema licenses technology in the US, and they joint own plants; they appear to be putting in the technology to make glycerin from rapeseed oil.

Metabolix

Metabolix make polyhydroxyl alkanoates PHA today, and they claim that their technology is a superior way to make 3-hydroxy propionic acid. They propose to take the crude PHA and cleave and hydrate it in one step to make acrylic acid directly. An advantage of the PHA route is that the PHA is easily separated from the rest of the cell. In fact it is not really necessary to kill the cells to harvest the PHA plastic. The yield may be 90% according to Metabolix. See also.

Metabolix says that their process is economical with oil at $90-100/gal. They say they could make butane diol just as easily.

It will be interesting to see who commercializes what first.

There has been work at making acrylic acid from lactic acid, which is 2-hydroxy propionic acid. The problem with that is that it frequently decarboxylates to give acetaldehyde as a side product. There has been lots of work on catalysts and processes to keep that under control. One promising route uses nanoscale phosphated zeolites.

Running Mechanics

2011-06-19T19:14:00.002-04:00

This barefoot runner is landing on her heel, but most
land on their toes. Citation.

Here is a fascinating post on running mechanics from Prof. Daniel Lieberman at Harvard.

It has some cool video, and the message is to land on your toes.

.

High Petroleum Prices Energizes Bio-butanol Projects

2011-05-17T18:20:00.000-04:00

Gevo's butanol process uses yeast and then a separation technology
to make a bio-fuel.

There were three bacterially produced butanol projects this week.

There is a pilot scale n-butanol plant being build by Cobalt Technologies in Alpena Michigan. Cobalt uses cellulose to make sugar which is fermented to butanol. We have seen that it is possible to bioengineer bacteria to make butanol instead of ethanol in the past.
In my view, fermentation to make chemicals is smarter than to make fuel.

Genomatica is working on a 1,4 butanediol technology. This is like the DuPont propanediol used to make DuPont Sonora, made by an e coli. This is on demonstration scale with Tate and Lyle.

Gevo has a process using yeast to make isobutanol. They are interested in fuel applications. There is very little information on their process available. It looks like a variant on fuel ethanol. Butanol is a better fuel than ethanol since it does not hold as much water.

Lucite Process for Methacrylate from Ethylene

2011-05-15T20:31:00.001-04:00

Strangely these "Lucite" PMMA plastic items were trendy
fashion pieces in 2010.

Lucite has developed a process, called "Alpha" for making methacrylic monomers from ethylene. (Lucite is owned by Mitsubishi Rayon.) This is significant because ethylene can be made from many sources including bioderived sources like sugar cane ethanol.

Construction of such a plant was started in Singapore in 2008. This plant uses syngas to make ethylene, which is dimerized, carboxylated and esterified to make methyl propionate, and then reduced to make MMA methyl methacrylate.

This is interesting because it is difficult to find renewable substitutes to methacrylates.

This is important since butylene has surged in price while ethylene has stayed cheap -- due to new natural gas supplies. By dimerizing ethylene they get around that.

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More on the Singapore plant which makes 120,000,000 kg/yr and is 30-40% cheaper to make and run. It uses ethylene, carbon dioxide and methanol.

Pepsi has a 100% Biodegradable Bottle

2011-03-23T19:50:00.000-04:00

Pepsi announced they will introduce a 100% renewably sourced PET bottle in 2012. The technology used to make the bottle is disturbingly unclear. It is a conventional PET bottle with similar molecular weight to standard.

PET bottles are made from ethylene oxide and terephthalic acid. There are a number of ways to get bioethylene including waste gas from landfills, dehydration of ethanol or heat treatment of biomass. Terephthalic acid can be made from lignin according the NREL via oxidation of p-xylene.

Wine Protects Against Gamma Rays

2011-03-20T07:46:00.001-04:00

In a sign there really is a God, the red wine chemical resveratrol has been proven to protect against gamma radiation. Resveratrol of course is the famous anti-oxidant found in RED WINE.

In truth he used the per-acetylated derivative, 3,4,4'-tri-O-acetylresveratrol which is shown in the figure at right. In the hydroxyl form, it is similar to other radical quenchers, like BHT.

Resveratrol is found in red wine. Also heath food
stores.

In a nuclear explosion, all three forms of radiation are abundant, but the gamma radiation is hardest to shield against. Oncologist Joel Greenberger of U of Pittsburgh speculated that chemicals that prevent oxidation would help, and they do.

The beneficial effect of wine and resvivirool in protecting against "nuclear fallout," hurts when radiation is given therapeutically to battle cancer tumors. This is because radiation tears up the body forming free radicals, and if oxygen gets to them quickly the free radicals become stable compounds. On the other hand, if the oxygen is absorbed by anti-oxidants, the damage may be repaired. Anti-oxidants help cancer patients feel better, but in doing so they reduce the beneficial effect of the drug on the tumor -- that is they help the tumor too.

Resveratrol is commercially derived from Fallopia japonica, or Japanese Knotweed.

Nothing Wrecks Renewable Energy Worse than a Recession

2010-09-18T14:29:00.000-04:00

C&E News is reporting that cellulosic ethanol development is floundering. This is because of the triple whammy of low corn prices (due to this year's bumper crop), low oil prices, and muddled government policies. I had not been aware that corn production was up this year, but there was rain in the grain-belt this summer, and acreage was up. Muddled government policy is par for the course, and screwy subsidies should be expected to continue. The government has not been releasing loans for prototype cellulosic ethanol plants despite being funded.

Cellulosic ethanol is ethanol made from sugars created by decomposing cellulose enzymatically. So far the central problem has been making the enzymes cheaply enough, but there are other problems too.

Shenhua Bets Big on Coal Chemicals

2010-09-05T13:04:00.001-04:00

Shenhua Group Logo

Shenhua Group (parent of China Shenhua Coal and Baotou Coal Chemicals) is investing in new coal gasification technology from Siemens and from Headwaters, new air separation technology from Air Liquide, and new polypropylene polymerization from Dow which will use their Unipol process, which is primarily gas phase process.

This fits another of my biases which is that when oil becomes prohibitively expensive, people will turn to coal, not to biofuels.

This follows the simple logic, of what did people use before they used petroleum: generally coal; I suppose whale oil will never make a comeback.

It is ironic because coal chemicals today are largely burned for fuel value rather than bothering to purify them for sale as specialty chemicals.

KL Energies Cellulosic Ethanol Plant Goes to Brasil.

2010-09-05T12:43:00.000-04:00

KL Energies Process

KL Energy of South Dakota is building a pilot scale cellulosic ethanol plant in Brasil with oil company PetroBras. This shows further maturity of the cellulosic ethanol line. This plant will use bagasse which sugar cane waste.

This project reinforces my opinion that biofuels are going to be based on tropical region feedstocks, because the agricultural productivity is so much greater there.

Exxon and Synthetic Genomics Algae Project Inches Ahead

2010-08-06T20:58:00.000-04:00

As reported a year ago, Exxon and partner Synthetic Genomics (a Craig Venter venture) opened a small test lab. They are also funding another $600 million for more work, which should by a lot of slime filled plastic bags. BP claims to have invested more ($1.5 billion,) but little has been heard about their developments.

This looks like marketing and public relations to me. I can't find any patents from these guys.

I still think it is surprising that the hard-boiled, oil-execs at Exxon are really investing in algae.

Links: Oilgea

Secret Gulf Oil Dispersant Finally Revealled - Corexit Composition Published

2010-06-19T06:52:00.000-04:00

BP has been using Corexit 9500 and 9527 ever since the beginning -- even though the government told them to switch. The composition has been the subject of speculation on my blog (31May) (23May) and elsewhere, but the EPA has finally published the composition. The difference between the two was supposed to be the solvent butoxy ethanol or EB, but it seems the actual difference is the ratio of ingredients.

CAS Registry Number	Chemical Name
57-55-6	1,2-Propanediol
111-76-2	Ethanol, 2-butoxy-*
577-11-7	Butanedioic acid, 2-sulfo-, 1,4-bis(2-ethylhexyl) ester, sodium salt (1:1)
1338-43-8	Sorbitan, mono-(9Z)-9-octadecenoate
9005-65-6	Sorbitan, mono-(9Z)-9-octadecenoate, poly(oxy-1,2-ethanediyl) derivs.
9005-70-3	Sorbitan, tri-(9Z)-9-octadecenoate, poly(oxy-1,2-ethanediyl) derivs
29911-28-2	2-Propanol, 1-(2-butoxy-1-methylethoxy)-
64742-47-8	Distillates (petroleum), hydrotreated light
*Note: This chemical component (Ethanol, 2-butoxy-) is not included in the composition of COREXIT 9500. Learn more about CAS Registry Numbers from the American Chemical Society

The highlights are that there are three deterents, and there are three solvents including one petroleum distillate, a ethylene glycol derivative and a propylene glycol derivative.

My previous post is here. My original oil field dispersant post is here.

A good site for the BP spill chemistry is the Facebook group Project Tantalus.

Span 80 = Sorbitan Oleate = 1338-43-8

||MSDS for Span 80.||
It is also called sorbitan monooleate. It is used in foods including ice cream and pickles.

Span 80 is a weak non-ionic surfactant with an HLB of 4.3 (low), and would be useful in emulsifying water into oil.

Polysorbitan 80 = 9005-65-6

||An MSDS for Polysorbitan 80|| Polysorbate 80 is routinely used in foods especially ice cream, and in medicine including flu vaccine.

Polysorbate or Polysorbitan 80 has an HLB of 14, which is relatively high for a non-ionic surfactant.

Tween 85 = polyethyleneoxide sorbitan trioleate = 9005-70-3

||Tween 85 MSDS here.||
It is also called polyethylene glycol sorbitan trioleate, or polysorbate 85.
This has an HLB of 11, which is intermediate. This is a large surfactant, which means it gives long term stability, but may not be as fast acting.

Metabolix Transfers PHA Genes into Switchgrass -- How Cool is That?

2010-06-12T16:56:00.000-04:00

Polyhydroxybutanolate, a PHA

C&E News is reporting that Metabolix, who sells the PHA polymer Miral, has successfully transferred genes to make PHA to switchgrass Panicum virgatum at a dry weight of 6% -- up from 3.7%. The PHA forms in the chloroplasts rather than in the cell walls. The research had previously been published in Plant Biotechnol. J. 2008, 6, 663.

Unlike polylactic acid, PHA's are (somewhat) hydrophobic and don't spontaneously degrade in water so one can make useful materials from them.

An opportunity/problem with them is that they are usually a mixture of different alkyl lengths, lengths that can be manipulated by controlling the feedstocks.

Metabolix has a 110 million pound plant in a JV with ADM called Telles.

Miscanthus giganteus, a relative of switchgrass
I can't resist reusing this picture though.

The problem with PHA is extracting it from the bacteria they are made from. This makes the price too high for common applications, $1.80-2.00/lb or $4/kg. The hope is new switchgrass based technique is that it will be productive enough to pay for the extraction.

The other prospect is that the waste products from the switchgrass production could be used in to make cellulosic ethanol or otherwise be enzymatically degraded to make useful chemicals.

Bioacrylic News

2010-05-31T06:49:00.001-04:00

Green Acrylic Acid is Still Acrylic Acid

Acrylic acid seems to be a material that could be made from renewable resources at reasonable cost and several chemical companies are exploring it -- though none commercially.

Arkema announced an $14 million alliance with two universities (LRGP (Laboratoire Réactions et Génie des procédés) at ENSIC chemical engineering school in Nancy, and MOPS (Laboratoire Matériaux Optiques, Photonique et Système) at Paul Verlaine university in Metz) to develop acrylic acid technology from glycerin. This is significant because Arkema is one of the big acrylic acid producers. Arkema had previously done work with a catalyst house on the process.

Arkema will look at the direct conversion of glycerin to acrylic acid, as well as the conversion of glycerin to acrolein (propanal) and use of conventional technology to oxidize acrolein to acrylic acid.

This is not new, Nippon Shokubai has developed catalysts for conversion of glycerin to acrylic acid.

Similarly Novomer has developed " acrylic acid by combining ethylene oxide, carbon monoxide, with a catalyst to make propiolactone," which is used to make acrylic acid by dehydration. Propiolactone is the cyclic form of 3-hydroxy propionic acid.

This is similar to the route used by NREL and OPX Biotechnology to make 3-hydroxy propionic acid. See my other post. They are using genetically engineered bacteria to make the 3-hydroxy propionic acid.

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Here is an update on the Dow JV with OPX Biotechnology.

Green Material PDO Plant Expansion at DuPont Tate and Lyle

2010-05-16T12:11:00.001-04:00

Dupont Tate and Lyle announced that they were expanding their Louden Tennessee 1,3 propanediol plant to 135 million pounds from 100 million pounds.

1,3 propanediol is used directly as an additive (Zemea) in cosmetics, but it is also used in Sonora polyester polymers. Polymers of the 1,3 propanediol are more flexible than the 1,2 propanediol or propylene glycol (which is made from propylene.)

1,3 propanediol

In the big picture, this 1,3 propanediol represents one of two chemical plants using enzymatic feedstocks to make chemicals, with Cargill Natureworks lactic acid being the other. Both plants have been expanded recently.

This shows that non-petroleum feedstocks can compete without subsidy, although in both cases customers are paying a premium to be using renewable feedstocks.

Bio-oil and Green Chemistry

2009-12-13T16:02:00.000-05:00

I wanted to move one of my favorite Green Chemistry posts from my general interest blog to here where it fits better.

Despite the low oil prices, work continues on converting waste biomass and cheap cellulosic sources like Switchgrass into fuel sources, so called bio-oil. It is fairly easy to turn waste biomass into gas by baking at 1000C. This product called synthesis gas is rich in hydrogen. It takes work to turn this back into a liquid fuel, which might be more convenient.

By baking at 500C, a liquid results, but the conversion is less than complete, and that is a waste of resources and energy.

The problem is that the cellulose is mixed with lignin, and the lignin is hard to degrade. Plus the combined ligno-cellulose is not very soluble.

Conrad Zhang of PNNL (Pacific Northwest National Labs and KiOR) says that lignocellulose dissolves in an imidazolium ionic liquid, and that once soluble it decomposes at 100C using copper chloride and chromium chloride as catalysts. This is a big break through if the other materials can be recycled. KiOR is working the Brasilian company Petrobras to develop the technology.

Of great interest in the chemical industry is the creation of feedstocks pure enough to use for producing chemicals. It appears that 5-hydroxymethyl furfural maybe one such chemical. C&E News reports that Hanson of the Technical University of Denmarkk can make 5-hydroxymethyl furfural from fructose by treatment with simply microwaves.

Of course the production of furfural from biomass is not new. Quaker Oats was making furfural from oat hulls EIGHTY-SEVEN years ago!!

As readers of my other blog know, furfural is found in the extract from oak barrels like those used for wine and for whiskey. Furfuryl is supposed to have a burnt taste, and 5-hydroxymethyl furfuryl is carmel tasting.

The oxidation of 5-hydroxymethyl furfural yields furan dicarboxylic acid, which could be used to make polyesters or nylon/polyamides. This could be interesting, and one could run reactions on the double bonds too.

In summary, there are not any new plants running new processes to make bio-oil, but ionic liquids show promise. Happily research in bio-fuels and bio-chemicals have survived the onset of the recession, and perhaps because of stimulus funding they will continue for a few years. It is just a matter of time until the world moves toward sustainable feedstocks for fuel and for chemicals.

See my next post on Green Chemistry.

Coatings in a High Petroleum Cost World

2009-12-13T15:29:00.004-05:00

This is my presentation before the Southern Society for Coatings Technology on Green Materials for the paint and coatings industry.

The link above works now. I apologize for when it did not.

Welcome to the New Depth of Processing: Chemistry

2009-08-30T14:26:00.001-04:00

This blog is dedicated to chemical and scientific issues, especially those that I deal with in my professional life. I want to put my public presentations on this page as well as general interest chemistry materials. For example, I am having a series of discussion on how physical chemical measurements can help people in our industry, the coatings industry. I thought that instead of, or perhaps in addition to putting these on Wikipedia, I could put them here.