## Dutch Consortium to Convert Methanol Plant to BioMethanol

##### 24 November 2006

A Dutch consortium is converting a conventional methanol plant in Delfzijl, the Netherlands, to produce biomethanol. The output—ultimately an estimated 1 billion liters (264 million gallons US) per year—will be directed to addressing the European Union’s requirement for a 5.75% biofuel component by 2010. Biomethanol can be blended directly into gasoline and serve as a substitute for MTB.

BioMethanol Chemie Holding (BV), a consortium of Econcern, NOM, OakInvest, Ir. S. Doorn and Ir. P. Hamm, purchased the plant from Akzo Nobel, DSM and Dynea.

The plant will be started up as soon as possible, initially producing fossil methanol as before. Modifications will be carried out over the next nine months, turning the plant into the world’s first bio-methanol plant. In the first phase, it will produce 100 kT [100 million liters] bio-methanol, a capacity that will be increased substantially in the following phases.

—Paul Hamm, temporary CEO of BioMethanol Chemie Holding

The plant will use a new process to make bio-methanol from glycerine, a byproduct of biodiesel production. Prices of glycerol have dropped due to the increasing supply resulting from rising biodiesel production.

Methanol (CH3OH) is the simplest alcohol, containing one carbon atom, and can be manufactured from a variety of carbon-based feedstocks such as natural gas, coal, and biomass. Worldwide, more than 90 methanol plants have the capacity to produce more than 11 billion gallons of methanol annually, according to the American Methanol Institute.

Most methanol production is a two-stage process that first converts a feedstock (often natural gas) into a syngas stream consisting of carbon monoxide (CO), carbon dioxide (CO2) and hydrogen (H2).

The second step is the catalytic synthesis of methanol from the synthesis gas. Each of these steps can use a variety of approaches and technologies.

2 CH4 + 3 H2O → CO + CO2 + 7 H2 (Synthesis Gas)

CO + CO2 + 7 H22 CH3OH + 2 H2 + H2O

If an external source of CO2 is available, the excess hydrogen can be consumed and converted to additional methanol.

The most favorable gasification processes are those in which the surplus hydrogen is oxidized to water, during which steam reforming is accomplished through the following partial oxidation reaction:

CH4 + ½O2 → CO + 2 H2CH3OH

CH4 + O2 → CO2 + 2 H2

The carbon dioxide and hydrogen produced in the last process would then react with an additional hydrogen from the top set of reactions to produce additional methanol. Methanol synthesis is highly exothermic, taking place over a catalyst bed at moderate temperatures.

Shortly after the announcement of the project early in November, Teijin Ltd., a global chemical company based in Japan, acquired a 25% stake in BioMethanol Chemie Holding (BV). Since its acquisition in 2000 of Twaron, a fiber originally developed by Akzo Nobel, Teijin has been active in the Dutch market and is now the largest Japanese investor in the chemical industry in the Netherlands.

Resources:

What's the difference between Methanol and Bio-Methanol?

Brad: AFAIK - basically nothing chemical (CH3OH). The Bio -Methane just comes from biological (poop,plants etc..) as opposed to geological sources (natural gas). The bio-methane would also tend to be cleaner in that it wouldn't contain as much additional junk. (sulphur, aromatics etc...)

Whoops - methane CH4, methanol CH3OH

Can methaonl be converted into ethanol or butanol ?
Or do you just blend it into gasoline.
Also is propanol any use as a fuel ?
Is there any simple way of turning natural gas into a liquid fuel - if so you might have something big.

Mahonj:

On this exact page on top left corner go to “topics” and click on “gas-to-liquids”. You will get the picture.

Hi,

Indy racers run on Methanol, I believe, or at least did at one time. And I wondered out loud why didn't road cars use Methanol once, and a chemist told me the incomplete burn byproduct of Methanol was Formaldehyde. Does anybody know anything about this? This was some years ago. Are vehicle catalysts and/or fuel injection better now to prevent this, or did am I remembering incorrectly about the Formeldyhyde.

The Butanol people are saying that Butanol has less HC emissions than gasoline.

The glycerine by-product from biodiesel production contains a methanol component derived from fossil sources, usually natural gas. Therefore, if the plant is simply recycling the methanol component out of glycerine from biodiesel plants, how can the end product be classified as biomethanol?

Isn't methanol more corrosive than ethanol or butanol? In the late 90s in New York City, the Metro Transit Authority had buses running on methanol but were found to have their parts being worn out more because of the fuel.

Donee, indy cars used to run on methanol, however they are moving over to ethanol over the next few years.

Formaldehydes form from the incomplete combustion of alcohol and gasoline. Alcohol produces more formaldehydes that gasoline specifically when an engine is running cold, warming up. My father designed a direct ethanol injector for American Bosch for a EPA project. While Formaldehydes were higher other pollutants were lower.

The fact that there is a second reaction that takes 4 H2 + 2 CO2 -> CH3OH + O2 is a hidden boon. Nearby gas/coal fired power plants may pipe some of their scrubbed exhaust CO2 to the methanol plant. This would result in increased methanol production, w/decreased CO2 output.
_This may be a moot point since gasifiers can use the syngas to make other fuels/chemicals.

When making SNG or methanol from biomass, there is usually a need for more H2, CO or CO2. There tends to be something left over that you could use if you just had.... If you need more CO2 you can get it from power plants. I see the future power plant as an energy plant, that makes liquid and gas fuels, as well as electrical energy.

Vin Diesel -

while it is true that the transesterification of triglycerides (aka vegetable oils and animal fats) does require methanol, it is not necessarily true that this has to be derived from fossil fuels. Part of the methanol derived from the glycerol residue could conceivably be recycled into biodiesel production, such that both it and the methanol would truly be from renewable sources. It's not clear if that is how the Dutch plan to to this, though.

Another ready source of biomethanol (aka wood alcohol) is the fermentation of forestry waste. Sweden and Finland comprise 2/3 of that industry in Europe.

While Sweden is a recognized leader in biofuels (ethanol), both the Netherlands and Finland are lagging behind on their commitments to the EU. Using biomethanol as a high-octane oxygenate would fit the bill, with a few caveats:

(a) it's far more toxic than ethanol, and in pure form burns with a nearly invisible flame. Extra safety precautions are required for handling it at blending facilities (and at NASCAR, btw).

(b) all hydrocarbon combustion processes produce some formaldehyde, but methanol more so than others. In the US, it is a restricted emission.

(c) the hydrogen-to-oxygen ratio in methanol is low, leading to low specific energy. This is acceptable in low blends but you pretty quickly fall fall of the maximum amount of oxygen permitted by law in regular gasoline and diesel.

(d) the vehicle fleet deployed in Europe features fuel systems that are less resilient to aggressive alcohols than their US counterparts (which have to meet CA summer gasoline formulations). This is another reason methanol blends would have to remain low.

Note that it is possible convert methanol into longer hydrocarbon chains via the Mobil MTG process. This is an alternative to Fischer-Tropsch but harder to control. The simpler process of catalytic chemical dehydration yields dimethyl ether (DME), a clean-burning substitute for diesel. Unfortunately, like LPG, DME has to be stored at mild pressures (8-10 bar) to remain liquid, making it too expensive to use even as an oxygenate for diesel.

Rafa-

You are the guru of the GCC forums...

Quick questions

1) You said methanol is toxic. Will pure methanol contaminate water in the same fashion as MTBE?

2) Why isn't MTBE simply being replaced with fossil methanol as an oxygentae? There are some huge methanol from NG producers out there (Methanex, etc.), so why aren't they putting up a fight to replace MTBE with methanol?

3) Paul Hamm, the CEO of the Dutch consortium said that "It (biomethanol) is a better, more cost-effective and certainly more environmentally friendly way to add bio-components compared to the usage of ethanol"... can you explain what he means by this? (in the production process, i.e. energy inputs, CO2, etc.)...

3) Biomethanol is CO2 neutral.

2) You can run M5 before problems occur.

1) Methanol will not contaminate ground water like MTBE.

www.methanol.org

Vin Diesel:

Methanol is toxic and even lethal only if ingested in big quantity (couple of shots). Unfortunately, it happens: methanol is undistinguishable from ethanol and many people died or got blind when mistook methanol for technical ethanol – looking for cheap booze. It is still a problem in Russia. In fact, many conventional alcoholic beverages contain small quantities of naturally occurring methanol. Surprisingly enough, the antidote for methanol is ethanol, so consumption of such beverages is perfectly safe.

Methanol is very fast biodegradable substance and does not pose any treat to the environment. In fact, about 30% of winter windshield washer is methanol – that’s why it does not freeze. No health effects or contamination from use of windshield washer was reported.

Methanol is highly corrosive to aluminum alloys. However, in small quantities (3-5%) together with ethanol and with some corrosion inhibitor additive gasoline/methanol/ethanol blends are safe for aluminum components (think intake manifold or engine head). It was used in US and Canada some time ago, but not now.

Your question why methanol is not used instead of MTBE is a good one. It puzzles me too. Methanol is way cheaper then ethanol, and could be produced on remote strained NG fields and transported in tankers form oversea to consumers – exactly what Methanex is doing. I believe that reasons why it is not used as gasoline additive are mostly political, not technological or economical.

Vin Diesel, Andrey -

methanol could indeed be used as a gasoline oxygenate but as I indicated, blenders would fall foul of the oxygen and density standards defined for Euro 95 pretty quickly. Both MTBE and ethanol are better fits. Paul Hamm's statements favoring methanol over ethanol I would describe as a bit of self-serving marketing spin, though not entirely unreasonable. Biomethanol is easier, i.e. cheaper, to produce than bioethanol.

MTBE is a suspected carcinogen. There were a number of cases of groundwater contamination in California, at gas stations with single-hulled storage tanks that ended up leaking due to corrosion. The US EPA decided last year to withdraw its requirement for MTBE in summer gasoline, prompting blenders to very quickly switch to the only alternative available in volume: corn ethanol.

In Europe, gas stations have been required to use double-hulled storage tanks for decades and, there have been no reported cases of groundwater contamination. MTBE is still used as an oxygenate here. That is one of the reasons why much of the biofuel industry here is focussed on biodiesel, which is cheaper to produce than bioethanol (except in Sweden, apparently). However, now that the WTO has curbed subsidies to farmers growing sugar beets for food, a transition away from MTBE may yet happen in Europe as well.

The U.S. deregulated NG years ago. I heard that the chemical industry in the U.S. was under pressure to move to where the NG prices were lower and more stable. To use methanol, made from a price volatile feed stock like NG was not as good as giving the farmers a $.50 per gallon ethanol subsidy. The farm lobby is pretty powerful and ADM donates freely to both parties. As far as picking MTBE over methanol 10 years ago..that is still a mystery to me. The reason the industry went with MTBE instead of methanol is that MTBE is cheaper. MTBE is produced from isobutylene and methanol, where isobutylene is a byproduct of the refinery that would otherwise be flared off or used for heating etc. I.e. the price of methanol (whose price in turn is determined by its feedstock NG) determines the price of MTBE, but for each liter of MTBE produced the refinery needs only about 0.35->0.4 liters methanol. See http://www.eia.doe.gov/emeu/steo/pub/special/mtbecost.html Thanks for all your responses about methanol. Some other questions: 1) Again, why is biomethanol cheaper to produce than bioethanol? What in the production process makes it cheaper? (a less complex carbon chain?) In Europe, ETBE is a popular gasoline additive instead of pure ethanol, especially in France & Spain. 1) Does ETBE contaminate groundwater like MTBE? 2) Since MTBE is cheaper to make than methanol, is the same true for ETBE vs. ethanol? If so, why isn't ETBE more widespread in the U.S.? 3) Why does the French gov't want ethanol to replace ETBE in that country? Thanks again... Thanks for the MTBE info. Congress did say they could use any oxygenate, so they picked the cheapest one. When you say bioethanol, do you mean fermented or cellulose or gasified? Each one has its own cost structure. It usually has to do with yield per input unit, capital cost and energy required. Methanol can gasify from biomass at a higher efficiency than ethanol fermented from corn. As for feed stock, corn goes for maybe$3 per bushel (56 pounds) so a ton would cost $100 or so. A ton of biomass goes for about$30. These are not exact numbers, but it gives you some idea. As far as ETBE, I do not have a clue.

Vin, SJC:

There is old, but quite informative article about why MTBE and ETBE are much easier to blend, transport, handle, etc. then straight alcohols:

http://www.ethanol-gec.org/clean/cf04.htm

As for bioderived alcohols, they are as a rule of thumb more expensive then synthesized from fossil fuel stocks. Possible exemptions are cane ethanol in Brazil and palm oil in Indonesia and neighbors. However, economics of these fuels is murky, because both cultures are very labor intensive and labor cost (and environmental constrains) in both South America and South East Pacific are increasing as their economies are catching-up with developed countries. Additional factor is that sugar cane plantations in Brasil, used currently for fuel ethanol feedstock grow, are practically excess acreage after shrinking of originally intended production of food sugar.

Why biofuels are produces on ever increasing scale? Two words: subsidies and mandates. And it is nothing wrong with it, because modern industrial biofuels are emerging technologies potentially able to substitute sizable amount of crude oil, and should be helped to the market until economy of the scale and next generation biofuel technology make them price competitive with gasoline and diesel without subsidies and hefty tax credits.

Its a wonderful effort to convert methanol into biomethonal which has a lot of advantages.

There are developments in DME/Methanol in China today:
Access to methanol, a key primary input, to manufacture DME , Xinao recognise this and JV with Methanex to grow the DME Business. While there are several technology developments recently for selective production of olefins, especially propylene either from methanol or from DME. UOP and Lurgi are fairly advanced in the technology. In fact Lurgi AG, will be sharing their experience at upcoming North Asia DME / Methanol conference in Beijing, 27-28 June 2007, St Regis Hotel. The conference covers key areas which include:

DME productivity can be much higher especially if
country energy policies makes an effort comparable to
that invested in increasing supply.
By:
National Development Reform Commission NDRC
Ministry of Energy for Mongolia

Production of DME/ Methanol through biomass
gasification could potentially be commercialized
By:
Shandong University completed Pilot plant in Jinan and
will be sharing their experience.