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I

NEW CATALYSTS, NANOMATERIALS AND PROCESSES

DEVELOPED BY NANALTECO S.L.

 

           

The team is focused on the following processes, including synthesis of nanomaterials, characterization and testing:

Adsorbents

  • Efficient adsorbents for water based on modified carbon or mesoporous silica; the materials can adsorb up to 80 wt. % H2O at room temperature and release water by heating at 70-80oC, i.e. they are better than zeolites (up to 30 wt. % H2O, release at T > 250oC)

  • CO2 storage materials with the capacity reaching 30-35 wt. % (better than monoethanolamine)

  • H2S and SO2 storage materials (25 wt. % and 45 wt. %, respectively).

  • Adsorbents for fine purification of gases and liquids (hydrocarbons) from thiols (concentrations lower than 10-20 ppb are reachable)

  • Specific MOF (metal organic frameworks) materials and related Mixed Matrix Membranes for separation of light gases

  • Selective adsorbent for removal of water from ammonia

  • Efficient air separation PSA material (better than low-silica X zeolite)

  • Materials for removal of ammonia from inert gases

  • Chemisorbent for removal of oxygen impurities from diverse gases

  • Adsorbents for cold start emissions (capable of holding toluene and other hydrocarbons up to 350C),

  • Adsorbent/catalyst for PCB removal in water and soil

  • Hydrogen storage in reversible catalytic cycles of hydrogenation-dehydrogenation of organic compounds (up to 7.5-8.0 wt. % of H2­), improvement of nanocatalysts for both stages and of the properties of the liquid organic hydrogen carriers (viscosity, boiling point)

  • Hydrogen storage in metal organic frameworks (MOF)

  • Separation of CH4/C2H6, CH4/CO2, CH4/C2H4, C2H6/C2H4 and other mixtures on MOF or COFs supported on ceramic membranes and mixed matrix membrane systems,

  • Selective removal of acetylenes and dienes by adsorption.

  • MOF Materials for conservation/storage of flavors/odors

 

Partial or complete oxidation of various substrates

  • Aromatics to phenols under supercritical conditions (oxidation with N2O, use of activating additives to N2O);

  • Propane conversion into acrylics (new approaches to activate propane);

  • CO2-assisted oxidative dehydrogenation of propane;

  • Complete oxidation of hydrocarbons and trace amounts of VOCs in vent gases at very low temperatures (perovskite-type catalysts, gold-based low-percentage catalysts, woven structured materials and foams);

  • Partial oxidation of dimethylether into dimethoxyethane (monoglyme),

  • Selective oxidation of ethanol into acetaldehyde (100% selectivity at 100% conversion), also oxidation of other alcohols into aldehydes

  • Oxidation of propanediol into lactic acid.

 

Hydrogenation processes

  • Aromatics saturation, including aromatics hydrogenation on sulfur-tolerant catalysts and separate hydrogenation of benzene in the presence of toluene;

  • Ring opening of cyclic aromatic or naphthenic compounds into aliphatic products;

  • Aldehydes to alcohols, including selective hydrogenation of unsaturated aldehydes using hydrogen spillover effect;

  • Dienes to olefins;

  • Acetylene and phenylacetylene hydrogenation into ethylene and styrene, removal of phenylacetylene in styrene by hydrogenation, cyclotrimerization, hydroamination or polymerization;

  • Hydrogenation of N-heterocycles;

  • Hydrodechlorination of CFCs and CCl4;

  • Hydrogenation of nitroaromatics;

  • Hydrogenation of polymers (C=C, C≡N, C=O bonds, aromatic moieties) on heterogeneous catalysts;

  • Selective hydrogenation of butyne-1,4-diol;

  • Hydrogenation of other functionalized derivatives,

  • Hydrogenation/hydrodeoxygenation of vegetable oil and fatty acids.

 

Renewables conversion

  • Glycerol hydrogenation into propanediols, propanol

  • Glycerol partial oxidation into acrylics

  • Reforming of glycerol, sorbitol and other polyalcohols and lignocellulosics

  • Transalkylation (methanolysis) of triglycerides

  • Dissolution and conversion of lignocellulosics under supercritical conditions (water, hydrocarbons, alcohols)

  • Conversion of lignocellulosics under microwave activation

  • Water reforming of sorbitol and mannitol, H2 production

  • Ethenolysis of vegetable oil (metathesis)

  • 3-Hydroxymethylfurfural hydrogenation

 

Methane conversion

  • Oxidative coupling on woven structured catalysts

  • Conversion into synthesis gas by methane partial oxidation.

  • Water gas shift reaction

  • Dry reforming and tri-reforming on structured metal catalysts (FeCrAl sintered metal fibers or foils)

  • Microwave-assisted conversion of methane (CO2-reforming with extremely low soot deposit).

 

Acid-base catalysis

  • Skeletal isomerization of C4-C16 paraffins;

  • Dehydroisomerization of n-butane into isobutene;

  • Nitration of aromatics into valuable products (nitrobenzene, p-nitro and p-dinitrotoluene, 1,5-dinitronaphthalene);

  • Dehydrochlorination of ethylene dichloride into vinyl chloride;

  • Alkylation of aromatic hydrocarbons and phenols (solid catalysts and ionic liquids);

  • C4 alkylation in ionic liquids and in supercritical isobutane

 

Other processes under investigation

  • Catalytic metathesis of functionalized olefinic compounds and unsaturated cyclic compounds (synthesis of alpha-olefins);

  • Aromatization of methane and ethane on zeolite and oxide (superacid) catalysts;

  • Hydroamination, alkoxycarbonylation, carbonylation, hydroformylation of long-chain olefins;

  • Electrocatalytic oxidation of sulfur compounds in ionic liquids;

  • Electrocatalytic polymerization of aromatics and heterocycles (synthesis of conducting polymers) in ionic liquids.

  • Conversion of CO2 into valuable compounds (carboxylic acids, olefins, CO, methane, methanol, higher alcohols).

  • Catalytic processes in supercritical fluids (hydrocarbons, CO2, alcohols, water): partial oxidation, depolymerization, alkylation, isomerization etc.

  • CO2-assisted gasification of coal with formation of CO

 

Nanomaterials and electronic materials

 

Synthesis and application of nanomaterials:

  • Nanoparticles of noble metals and alloys in zeolite, oxide and carbon matrices;

  • Nanoparticles of semiconductors (oxides like SnO2, chalcogenides like CdSe, and other materials like GaN) encapsulated in microporous and mesoporous matrices

  • Nanomaterials on the basis of electro- and proton-conducting polymers;

  • Catalytic nanocomposite materials for hydrogen storage;

  • Ionic liquids, including Si-containing ionic liquids with an extremely low vapor pressure for application in open space as heat transfer agents;

  • Sol-gel inorganic materials (mixed oxides),

  • Structured catalysts and other nanostructured materials (nanotubes, nanorods) on metal carriers (gauzes, foams, foils)

  • MOFs as electrode materials for the application in Li ion batteries and supercapacitors or as precursors of nanostructured carbon and oxide compositions

 

Nontraditional methods of activation (in-situ and ex-situ)

  • Cold plasma

  • Microwave activation (2.45-10 GHz, resonator-type reactors),

  • Sonication

  • Irradiation with electron beams.

 

Tremendous enhancement of the activity of diverse catalysts in various reactions (aromatics hydrogenation, dehydrogenation of naphthenes, cracking and isomerization of paraffins, paraffin alkylation and some oxidation reactions) was unraveled while studying the effect of cold plasma, microwave activation, and electron beams on the catalyst performance.

 

New hydrogen storage materials with the capacity of about 7.5 wt. % of H2 have been invented, they are much more efficient and cost-effective than both intermetallic and nanotube hydrogen storage systems.

 

A combined process was developed in which aromatics saturation is coupled with ring opening and paraffin isomerization. Very high yields of isoparaffins were achieved in this process. Also, of particular interest is the process of partial isomerization of higher paraffins to produce monobranched isomers (the problem of winter quality diesel fuel). The process of separate hydrogenation of benzene in the presence of toluene is being developed in the recent time.

 

Room-temperature ionic liquids are new ecologically friendly green solvents and catalytic media; they represent molten salts containing an organic cation (for instance, alkylpyridinium or alkylimidazolium ions) and an inorganic anion (such as chlorometallate, tetrafluoroborate, hexafluorophosphate, triflate etc.). These unique compounds are non-flammable, non-toxic, and non-volatile (no vapor pressure) and exhibit outstanding electrochemical behaviour, interesting solvating properties and intrinsic catalytic activity. They are already proven to be good catalysts for olefin oligomerization and some other processes. They show promise in the future applications in the following processes:

  • Oligomerization of olefins, in particular dimerization of n-butenes, isobutene, and propene;

  • Disproportionation and skeletal isomerization of paraffins C4-C16;

  • Aromatics alkylation with olefins;

  • C4 alkylation with butenes;

  • Isomerization of cyclic saturated hydrocarbons, including terpenes;

  • Metathesis of olefins and functionalized olefins, including vegetable oil;

  • Hydroformylation of olefins;

  • Gatterman-Koch carbonylation of aromatics;

  • Nitration of aromatics;

  • Isomerization of alkanes,

  • Removal of sulfur and nitrogen compounds from hydrocarbon mixtures;

  • Hydrogenation of organic compounds;

  • Oligomerization of benzene, biphenyl, aniline and pyrrole into polyphenylenes, polyanilines and polypyrroles, synthesis of conducting polymers;

  • Electrochemical applications of ionic liquids (selective oxidation of various substrates, polymerization of aromatic and heterocyclic compounds; electrodeposition and electropolishing of metals, CO2 reduction).

  • Synthesis of metal and metal oxide nanoparticles in ionic liquids

 

The team developed original non-volatile ionic liquids with an extremely low vapor pressure (below 10-11 Torr at room temperature and below 10-3 Torr at 550 K). These unique ionic liquids can be used in open space as heat transfer agents or as non-volatile ionic liquids in SILC (supported ionic liquid catalysts).

New reactions and applications of ionic liquids either as catalysts or catalytic media (solvent and cocatalyst) can be explored taking into account the interests of a potential industrial partner.

 

Synthesis of novel materials includes nano-sized carriers and adsorbents, in particular, materials for CO2, CH4 and O2 storage. In the case of CO2 storage, the capacity close to 30 wt. % has been achieved, which is better than for the conventional monoethanolamine system (~10 wt. %). For methane, ethane and oxygen storage, Metal Organic Framework (MOF) materials have been designed with capacities of about 0.5-0.6 g of the adsorbate per gram of the adsorbent.

 

The team is capable of performing customer service related to characterization of diverse materials (catalysts, adsorbents, nanomaterials) by modern physicochemical methods, including DRIFTS, UV-VIS, ESR, XPS, XAFS (EXAFS, XANES), TPR, TPD, TGA/DTA.

 

The experience of the team is well documented in open publications, patents and is proven by long-standing collaboration with industrial partners in many areas of catalysis and materials research. The laboratory is interested in the partnership / contracts with potential partners to complete the research programs and to jointly develop efficient materials and processes with a good potential of further commercialization.

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