Technologyreport

Removal of carbon dioxide from carbon dioxide-hydrogen mixtures with amino functional polymer membranes and investigation of transport and reaction processes in carbon dioxide polymer systems

Mecadi GmbH

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Preamble

Mecadi- MEmbranes and CArbon DIoxide – Permeation and Polymers

A Review and an Analysis of the Trends

Ten years ago, as the work on the technology report for the separation of carbon dioxide from gas mixtures began at the research centre in Karlsruhe, the use of methanol as a fuel and the on-board reforming of hydrogen was in the pre-developmental stages.

The purpose of this study was to find alternatives to using methanol as a chemical hydrogen accumulator. Carbon monoxide, as a by-product of methanol-reforming, limits the lifetime of the anodes in the liquid fuel cells because it is a catalyst poison. Formic acid, however, only produces carbon dioxide and hydrogen when used for reforming. The study has also shown that formic acid is also limited because of the gases resulting form this separation, carbon dioxide and hydrogen.

Today, ten years later, on-board reforming is still not being used in series, but the topic of fuels is more current than ever. Hybrid vehicles with electric motors have successfully been brought on to the market by Asian manufacturers. Bio-fuels, mixed with petrol and diesel, are currently being discussed in the political world. It was decided by EU regulation to add a mixture of 20% renewable raw material to fuels until 2020. The substance concerned was ethanol, that is plant oil esters.

The late discussion about possible side-effects is surprising, although many studies and experiments on the aspects of such a regulation have been being published for years, by among others CARB (Californian Air Resource Board). More simply expressed: if you add 10% bio-ethanol to petrol, then ten times the amount of fuel penetrates through an intact gasket into the environment. This has been proved by vehicles produced in series, building parts and materials. However, there are materials which do not show such effects, but existing vehicles are not equipped with these materials in series production. This is not necessarily because of the price of these materials, it is simply because there was never a demand for this in the past. During the discussion further unpleasant side-effects also came to light, like the competition of energy plants as food as well as ecologically-balanced products in which not everything is biological which says biological on the label. Trends set here are second generation bio-fuels. Whole plants are changed into fuels, using pyrolysis and cracking, which is the breaking down of the plants of the plants into small reactive components and following this the construction of specific chains. Due to the development of the production process, the auto mobile manufacturers now have time to test components or if necessary to adapt or develop the existing fuel systems. With the prognosed decrease in the availability of crude oil, this utilization of plants is getting competition from industries that need new carbon sources for their products, like for example, the chemistry industry after the mineral oil age. New ways of synthesis and classes of products have resulted from this.

For our mobility and energy supplies, there will be no way of getting around the solar-based hydrogen industry in the long-term. The tools which are used for this are the following: The technical availability of hydrogen is like finding the eye of a needle. Whoever develops the platinum-free electrodes for water electrolysis without an electrical surge in hydrogen has the potential to become as rich as Bill Gates.

But what came of the ideas from the technology report ?

At about the end of the year 2000 the following technological building blocks already existed: The purpose of the foundation of Mecadi, whose name was created from the words: membranes, carbon and dioxide, was to make use of this knowledge. The name was chosen from a number of different suggestions at a round table meeting in Professor Dinjus' office in Karlsruhe at the beginning of 2001. The domain and brand names were available. Research on the internet only revealed a Belgian footballer with this surname and also no meaning for this word could be found in any other language. At a later date, only one namesake was found, a Belgian company that manufactures machines for the plastics industry.

Several key events at the start led swiftly to Mecadi's direction as a research and development service provider in the permeation field. During the foundation phase it already turned out that it would not be possible for us to start up and finance a membrane manufacturing company on our own. A business plan for the manufacture of membranes for the separation carbon dioxide was not possible with conventional funding. Today's buzzword carbon dioxide was not familiar to the bank clerk, at least not in association with environmental protection and renewable energy, until the funding discussion.

A five-year development period for a product and ten years until a breakthrough was rather suspect, so that the discussion on the bank's part quickly developed in the direction of a deposit in a savings account as security for the company credit card. The expensive venture capital financing with necessary returns of between 10 and 30% of the capital used (to pay the interest) wasn't acceptable, because of the capital already available to the company. These return assumptions are only representable in the rarest cases, it is mostly necessary to have new capital before the first investors drop out. The customers' evaluation was even more important. This was a comment made after a presentation in the research centre of a big oil company:”Good, using your technology we will save 20% of the energy used during a procedure on the off-shore platforms, but do you also have helicopters in order to service the equipment?” We were hardly back in Germany when we received an inquiry for our service of permeation measurement of hydrogen under high pressure. In order to offer this as a service, the appropriate knowledge should also be available.

This service business grew continually and was enhanced and improved to suit the customers.

The compound carbon dioxide, which was unknown to many up to now, has meanwhile become a key word in the media. This is shown by more and more inquiries which are coming in, for example: Is it possible to buy the membranes for the separation of carbon dioxide? When is it sensible to use such membranes in general? The seemingly sensible answer is everywhere where money can be earnt by using them. This means if only carbon dioxide is produced as a product because this is forced by legal conditions, then this can lead to the moving away of branches of the industry in the short-term. A current example of this is the large-scale carbon power plant planned in Ensdorf in our coal-mining region of Saarland, which is to be powered by coal imported from China. Now according to media reports, a location in Greece is favourised.

Things look different when you look at the topic of bio-gas. Here, there is the demand to separate carbon dioxide from methane in order to generate a utilizable combustion gas. The renewable energy law (EEG) makes it possible to establish new technology in a subsidiary market. But the aim must be to be able to produce methane a marketable price. In this case membrane systems have great potential, but the guarantee of durability is risky. The fermentation medium of changing gas impurities, particularly sulphuric compounds, reduce the permeation rates and the selectivity of the membranes in permanent operation. New technological developments like ceramic hollow fibres or special polymers as separation layers could cause a breakthrough. These membranes would also have the possibility to simultaneously remove carbon dioxide, water and hydrogen sulphide from the methane produced. However great the potential of this field of work may be, the real money lies in gas. Why should a membrane manufacturer or a plant manufacturer who reads the gas metres not be paid per unit of gas produced?!

Mecadi – from service provider to manufacturer. On a smaller scale we have already taken this new path, as we are testing and developing new ways of particle collection for air surveillance, so as to bring it out on the market as our first product.

The physical growth of Mecadi has also led to a continual rise in the need for work space. In order to fulfil this demand, we are planning to build a new building for our company. Membranes and carbon dioxide “Permeation and Polymers” - it remains exciting!