Nanotechnologies and new materials Project presentation THE MOLECULAR SIEVES FOR GAS SEPARATING MEMBRANES R. A. Denissov A.V.Chernyshev S.A.Yakushev Membrane - a partition dividing volume on two parts. The membrane. Last years, in arising of ecological and energy problems, there has appeared couple of technologies - «zero emission fuel combustion» where the central point takes burning fuel in an atmosphere of oxygen - complete combustion. Products of complete combustion are H2O, CO2 and inert components, thus the thermal emission increases that allows to save fuel or use lowcalorie one. There has appeared need of scale oxygen production Fig.1. The basic operating diagram of air separating membrane p1, p2 - pressure. If no nitrogen gathering there is more simple design, the membrane operates under rarefaction. The physical principle of separation is based on indication of oxygen and nitrogen structural properties distinguishing. In particular, because of kinetic diameters difference (O2 ~ 3,46Å, N2 ~ 3,64Å), being smaller one oxygen can faster move in a membrane material, and, hence, has being collected a lot in the other volume, it’s a principle of different resistance to motion. Small diameters difference (~8 %) does air separating process fine. There is a rule: the higher separation level the fewer throughput. Decision searching. The most widespread cryogenic way of oxygen to produce (air freezing in -150Cº lower) implies a single oxygen factory that is expedient for the big consumers, but is unacceptable for middle and small ones, in particular, in transport. There are searching the way in development membrane technologies air separating as continuous process to get and use oxygen on a site (in situ) and with no storage (cylinder). . Intensive development of small molecules membrane separation technologies was in 60th years. Also it has been caused by necessity of independent lifesupport conditions to create in underwater and space vehicles (noneconomic reasons). As a membrane the continuous material has been used to be thin ~1µm polymeric film, which surface takes hundreds square meters in a single module. With the beginning of ХХ1 century, in connecting to energy and ecology problems (economic reasons), there was a big interest to membrane technologies possibilities and their new areas application. The attention had focused on: - development of new, low sized design decisions using a polymeric film; - creation of the new materials to give new separation quality and capable to operate in wider range of conditions. The projects of prestige 1.Polymer membrane. Japan, Matsushita polymeric membrane. It is submitted on the market, as the conditioner making raised oxygen concentration (~27 %) in automobiles gas-polluted streets located apartments. Design: there are frameworks covered by polymer film united in module. It’s advanced and market adopted 60th year’s development. It operates under rarefaction, takes outside air. https://industrial.panasonic.com/ww/products_e/product_cat2/AYD0 000_e/AYD0000_e.html The USA, a polymeric membrane Transportation Technology R&D Center of Argonne National Laboratory. There is in automobile air filter place. Air enriched by oxygen (have no data it could be accepted about 1.5 times) is used for a fuel charge preparation. It allows improve fuel combustibility and as consequence, "exhaust" parameters, to increase power. Other separation component - nitrogen goes to a spark arrester and further, in plasma mode, mixes up with exhaust gases, restoring toxic nitrogen oxides so up to molecular nitrogen as oxygen. A membrane are been polymeric pipes walls mounted parallel in cylinder module, analogue of 60th year’s development. It operates in excess pressure. It’s commercialization stage. Project almost completed, is in test. http://www.transportation.anl.gov/research/engine/air_separation.ht ml 2.Composite membrane. The USA, Praxair Inc composite membrane has ionic (complex minerals with oxygen sublattice) and electronic (metal) conductivity to use in powerful combusting plants. It’s a commercialization stage. It has no close analogues. It activates at temperatures 700 1000 °С (arranging in gas burning furnaces directly), it is made as pipes ~ Ø3 sm in length of ~3 m. The best concentration of oxygen is 99,5 %. Basic problem is in composite gas-resistance. http://www.gasification.org/Docs/2002_Papers/GTC02037.pdf http://gcep.stanford.edu/pdfs/RxsY3908kaqwVPacX9DLcQ/kobayas hi_coal_mar05.pdf Italy. Politecnico di Milano are being studyed composite membranes also. 3.Zeolite films. The USA, some of research groups, a membrane made as a polycrystalline zeolitic film. It has no close analogues. The basic idea is the use of porous zeolite crystals as molecular sieve. Having a small surface, the sieve has high throughput and good selection. It does a membrane universal for the widest applications and others competitive. The approaches are: zeolite microcrystals are been growing on a porous substrate, intervals between them are filled by polymer or, as the same the crystallization has been repeating, all of these is calling a membrane. The basic problems are in a non-dense, film low mechanical strength. http://www.cems.umn.edu/research/tsapatsis/ http ://www.aps.anl.gov/Future/Workshops/Membrane_Science/Presentat ions/Tsapatsis%20.pdf http://www.colorado.edu/che/FalcGrp/research/zeolite.html http://www.cems.umn.edu/research/kokkoli/pubs/Nat%20Mat.pdf These projects execution will put big economic and social consequences. Zeolites and air separation. Zeolites are porous strong alumino-silicate crystals having very complex structure, which element contains many tens of atoms. Their correct formed pores, incorporating each other through "windows", make a through channels correct network inside crystals (galleries). Fig. 2. Pores of synthetic zeolite A forming the channel. Being attach the same figures to others 8terms "windows" there is come out crossed channels three-dimensional system -calibrated through apertures molecular sieve that is favorable for fine separation. Quadrupole interaction is features of the nitrogen molecule structure, indicated zeolite cavity inside and there is selection strong factor. Fig. 3. The Y and NaA zeolites crystals surface in nanoscale, the area of "windows" makes ~7 % - Y and ~9,5 % - NaA, window diameters according are 7,4Ǻ and 4,2Ǻ (subnano). We consider air separation physical model in zeolite channels. Process of selection is defined by three simultaneously acting mechanisms: on input "windows" (1), at movement inside zeolite (2) and stronger nitrogen molecules quadrupole interaction with zeolite lattices cations (3). All of them act for the use of oxygen, as permeate (membrane through gas), that implies a high separation level of a mix. Changing zeolites and their structure it is possible these mechanisms to operate. Our works with Zhdanov zeolite show the zeolite complex alumino-silicate framework is capable to be reconstructed with structure conservation, i.e. to be in recrystallizating processes where single grains growth or reduction is in free space between them filling and strong couplings forming. Such a complex systems recrystallizating processes discovery and their real time activation possibility is an event in experimental mineralogy. It means also to have a basic opportunity to get dense polycrystalline forms with other zeolites too. The problem and proposing decision. The problem of zeolitic membrane to create as a homogeneous, dense material to get is caused by complexity of zeolites structure, it is a reason them to have no liquid and gaseous state. Good structure has pure artificial zeolites only, and they are synthesized as single microcrystals, the sizes ~1µm, and do not form films. Natural zeolites are polluted by impurities and other forms. In the beginning of 80th we had been developed polycrystalline monoliths technology producing from Zhdanov zeolite powders ("window" - 2,2Å) and it deriving non-stoichiometrical sodalites numbers, keeping physical properties of initial microcrystals. Then method and substance was got the USSR patents and patents of Japan, the USA, England, Italy, France, Germany and Sweden also. Photo. A monolithic polycrystalline Zhdanov zeolite plate of 0,3 mm thick: it is optical transparent, the density corresponds to crystal, being much better than 99 %, mechanical properties is close to glass, vibration-proof, allows mechanical clearing and washing, all a range of temperatures keep intact. The proposing decision: having suitable for air separating channels zeolite powder is pressed to make glass-like, having initial microcrystals structure monolithic block. Further it will be cutting for some plates and using them as membranes. Some applications and markets. Healthcare. In some estimations to satisfy superfluous oxygen personal needs the zeolitic membrane device can be placed in dimensions of a match box. The membrane also will protect from a dust, the microbes, and unpleasant smells, poison gases (ultrafiltration or deactivation by oxygen surplus). It can be used not only in single purposes and conditions, but to become daily accessory of each person, to change style of life. Sports. There’s sportsmen’s organism rehabilitation after trainings. Food stuffs. Food stuffs process and store in nitrogen inert atmosphere. It’s water saturating by oxygen in fish facilities. Power and transport. Due complete combustion it is possible to get about 20 % addition of energy at toxic emissions absence. Oxygen concentration increasing the combustion process is intensified; it opens abilities to use different new kinds of fuel, including biofuel and dust, with no any of essential preparatory transformations. The industry. Motor industry. There are industrial wastes deactivating, including sewage and emissions in atmosphere. There is creation of new technological processes and devices in applying of oxidizing reactions, nitrogen inert atmosphere and atmosphere to be free of dust, microorganisms and the other pollution, inaccessible by other ways. There is separating of other mixes, water desalinating. Architecture. Houses heating (boilers, furnaces, fireplaces). There is apartments conditioning. Stock-rooms and storehouses: there are preventing of ignitions and spoilage at long-term storage in nitrogen atmosphere. As adsorbents, powder zeolites occupy about 100 application fields. Market emergence of simple and cheap membranes will create an opportunity for mass engineering creativity and will cause a new turning of progress. Spheres of application variety and extensive and free markets together will define project innovative attraction. Consumers of simple independent devices having membrane central element can be private persons, small and middle-sized companies. This circumstance will allow begin manufacture and sale of production, being irrespective to innovation ability level of the large companies. “A technology breakthrough in separation processing is crusial to hydrocarbon industry…The end effect would be about 75% energy reduction in production and about 60% capital reduction” (From Sandia National Laboratories US DOE Report, 1999) http://www.ms.ornl.gov/programs/energyeff/aim/annual/98sec34.pdf Cracking membrane (project developing prospects). Necessary condition of a high-grade ignition mixture preparing is good fuel vapourability. This fuel should be made of small molecular weight hydrocarbons. Therefore oil is treated by cracking - decomposition of heavy hydrocarbons on easy ones as a result of couplings C - C breaking. Inside a zeolite cavity, in conditions of crystal field acting, breaking hydrocarbonic molecules C - C couplings is easier (operating time 3 seconds less). Therefore they are used as the catalyst in cracking. In an existing variant, zeolite microcrystals, as granules in porous binding are brought in an oil reactor (550 750 ºС), zeolite pores are sated by hydrocarbons. Formed as a result of couplings breaking easy molecules are leaving zeolite and mixing up with other mass which further is separated on fractions. Application of zeolitic membrane will allow to carry out cracking and separation in one process – operation analogue of a «molecular meat grinder» which processes heavy hydrocarbons to (CnHm) "forcemeat" of easy and flying ones. In operating it will be a boiler with a window - membrane. Such a 1 litre capacity boiler taking oil refining function, placed in motor compartment, will make automobile as “omnivorous”. Fig. 4. The combustion diagram where applying cracking and air separating membranes. Clusters in zeolites (project developing prospects). Powder zeolites pores inside it is possible to create and very high dense to place the structured groups of atoms – clusters (being impossible zeolite outside) which have unique optical, electric, magnetic properties. Then, during the recrystallizating pressing do these ones "to seal" as optical transparent dielectric monolithic polycrystalline block. These are materials for optoelectronics. We developed this way in Zhdanov zeolite works (cluster point defects as memory cells). In result there has been created optical transparent media series for reversive recording, storing and displaying information having screen imaging possibility. ”Dark trace” recording contrast comes nearer to black ink writing on a white paper (a history of matter). Information recording and storing media (see a photo also) were exhibited at the Exhibition of National Economic Achievements of the USSR. Work is awarded with a medal named as In achievements of national economy of the USSR. Fig. 5 Structure Zhdanov zeolite which some pores contains alkaline-halogen clusters having various point defects, Na3Al3Si3O12 (NaHal) х, where 0 <х <1 (from the old publication). Publications: Project examining. The team. 1. Roman Denissov, Sergei Yakushev. “The molecular sieves for gas separating membranes”. – Portal: SCIENTIFIC FRONTLINE , Oklahoma City, Oklahoma USA 17.01.2007 (Short issue April of 2006). The project has been submitted to Competition of Innovating Russian 2007/2008 http://www.inno.ru, carrying out by supporting by Ministry of Education and Science (the Minister is the Competition Council member) and Government of Moscow City. The project head: Denissov Roman Alexeevich PhD of physics Speciality: solid state physics Developed Zhdanov zeolite monoliths to get technology - the base of the project. Estonia, Tallinn, hot.ee@romulus1 Personal site: http://www.hot.ee/romulus1 http://www.sflorg.com/abstracts/ab090206_01.html 2. Р.А. Денисов, А.В. Чернышев, С.А. Якушев. «Молекулярные сита для газоразделительных мембран». – Portal: NANO NEWS NET, Russia, 4.10.2007. http://nanonewsnet.ru/articles/2007/molekulyarnyesita-dlya-gazorazdelitelnykh-membran 3. “The molecular sieves for gas separating membranes”. – R. Denissov personal site : http://www.hot.ee/romulus1 (RUS, ENG). 4. “The molecular sieves for gas separating membranes”. – Abstracts of Scientific and Technological Sections, Nanotechnology International Forum December of 3-5 Moscow, V.1, p. 583-584 (rus, eng). "White book” nomination, part: «Nanotechnologies and new materials». Competition is accepted projects determining scientific and technical progress in all spheres of activity (11 parts, the general competition), their examination and ranging are carried out, and a database is made. The project is in Competition final. There is a short list of 570 qualified ones. Chernyshev Andrey Viktorovich PhD of physics Speciality: physics of semiconductors and dielectrics Russia, S.-Petersburg anchernyshev@mail.ru Yakushev Sergei Alexandrovich The engineer Speciality: radio electronics Estonia, Tallinn, sergei.yakushev@mail.ee The conclusion. Our works on creation of monoliths left behind the time. Till now Zhdanov zeolite monoliths remain unique. The reason of such things should be considered not fundamental problems only, but as the nanotechnology opportunities interest and new needs have been arisen with a new millenium beginning only. The nearest analogue and, the most perspective to other materials, being grown as films molecular sieves have many of intercrystalline passes and in this reason are not suitable in fine air separating process. Even, the technology to get dense films will be created; the next will follow these ones operational stability problems. This weakest point is diverse materials interfacing (zeolite - substrate) which is unreliable to have no interpenetration transitive zone, the last one is been out this case. This circumstance isn’t intended in operational condition wide range as: high temperature, chemical factors, various mechanical influences, including vibration. Besides films (thin and fine) always has a surface clearing problem. All these shortcomings are not for a monolith. Recrystallizating pressing - direct technology to form monolith, eliminating intergranual cavities and passes. The proposing decision as zeolite polycrystalline monolith is novelty, high operational properties and, probably, - the only way of a molecular sieve sizing suitable for wide application to get. The present project is 4-th big project membrane air separating and a new breakthrough way to create predetermined property materials: Monolithic polycrystalline zeolites having free and nuclear clusters filled pores. Membrane researches and developments will borrow ~10 years or more. There will need to found target laboratory (the research center), manufacturing of the unique equipment and other research groups to draw. June of 2007, Tallinn-Kuusalu First issue –november of 2005, unpublished variant – 1992.