High-tech systems and materials

Andrey Yaroslavtsev

Kurnakov Institute of General and Inorganic Chemistry RAS Topchiev Institute of Petroleum

Synthesis RAS

November 15, 2011

Positions of Russia in R&D: ratio of needs and capacities

Индекс рыночной перспективности(динамика рынка и конкурентные преимущества продуктов)

Инд

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кого

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их р

азра

бото

к(о

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тста

вани

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в о

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&D

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Index of demand perspective

Transducers and sensors

Liquid mediums

Catalysts

Ceramic materials

Composites

Crystalline structures

Devices

Metals and alloys

Coatings and films

Polymers

Sorbents, membranes and filtersLife systems

Electronics

2.1. Sensor materials-nanomaterials for miniature highly sensitive sensors with high selectivity;

2.2. Materials for Energetics hybrid membranes and bimetallic catalysts for fuel cells; nanomaterials for new generation of electrochemical power sources; catalysts for the processing of high quality fuel.

2.3. Optical materials and materials for light production nano-structured optical fibers.

Hierarchical optical chemosensory materials

Electron microscopy, 220×160 m

ASM, 20×20 m ASM, 3×3 m

TEM, 0,4×0,4 mп-Xylol

50 ppm25 ppm

10 ppm5 ppm

2,5 ppm

Scheme of hierarchical sensory material structure

PHOTOCHEMISTRY CENTER OF RAS

10 ppm

50 ppm

10 ppm

50 ppm

Intensity change of 420 nm wavelength in the presence of various

concentrations of benzene

Intensity change of 420 nm wavelength in the presence of various

concentrations of n-xylene

benzene n-xylene

1 23

4

5

6

7

8

9

10

111213

14

15

16

17

18

19

20

21

2223

0

500

1000

A1 A2 … An Вmultivariate

analysis algorithm

V

X1 X2 X3 … Xn

Multi - electrode system (including special membrane electrode) based on biocompatible nanosensors to measure the freshness of beer

sour

stale

fresh

?

Voronezh State University, IGIC RAS

Similar systems can be used for the analysis of proteins, drugs, blood etc.

Diagram of beer

responses

3D thermocatalytic Gas Sensors (pellistors)

Characteristics: Т = 360 ÷ 590 °С С = 0 ÷ 5 % vol. СН4

Sensitivity 15 - 50 mV/% vol. СН4

Power consumption 75 - 200 mW

MSU, Department of material science

Determination of methane

concentration in coal mines

Electron microscopy of MF-4SC membrane (Russian analog of Nafion ), modified by silica (in situ synthesis), particle size 2-5 nm

7

Temperature dependence of conductivity for MF-4SC membrane

modified by acid zirconium phosphate (a-e). Comparison sample (f).

Ion conductivity as a function of RH for MF-4SC (1); MF-4SC+SiO2 (2); MF-4SC+SiO2+HPW (3) and MF-4SC+SiO2+CsHPW (4).

Kurnakov Institute of General and Inorganic Chemistry RAS

Hybrid membranes for fuel cells

Cathode materials for lithium ion accumulators

Electron microscopy of LiFePO4 composite

with carbon.

Comparison of cathode materials

Kurnakov Institute of General and Inorganic Chemistry RAS

Discharge capacity, mA/h

Rate of discharge/charge

Discharge

Charge

Charge-discharge curves (4-th cycle)

Traditional material Charge process

LiCoO2 Li1-XCoO2

(CoO2)

Fiber Optics Research Center of RASBismuth-doped fibers for lasers and optical amplifiers

The broad band of luminescence in Bi-doped fibers enables one to develop fiber lasers and amplifiers in the wavelength region uncovered by effective rare-earth active media.

Recently developed Bismuth-doped fiber lasers: spectral lasing region

and maximal CW output power.

2.6. Nanoscale catalysts for deep processing of raw materials nanostructured and nanoscale catalysts for petrochemical processes; catalytic conversion processes of natural gas and oil associated gas into

liquid fuels, hydrogen and valuable organic products; catalytic methods for processing of renewable raw materials (biogas and

biomass) into valuable organic products.

Nanoheterogeneous and nanostructurated catalysts for hydrocarbon feeds transformation

Metal – organic frameworks

Hierarchic oxides systems

Catalytic processes for natural/ associated gas

conversion

Nanoheterogeneous catalysts

HYDROGENSYNTHETIC

FUELSCHEMICAL PRODUCTS

Heavy oils, bitumens, heavy residues conversion

HYDROGEN FUELSLIGHT

OIL

Topchiev Institute of Petroleum Synthesis RAS

CATALYTIC CRACKING OF VACUUM GASOIL

The advantages of new technology : Flexible processing of vacuum gasoil Processing using gasoline mode:

Gasoline (<205оС) yield – 56% mass. Overall yield of propane-propylene and butane-butylene

fractions, gasoline and light gasoil – 87,5% mass.

Research octane number – 94,2 Consumption of fresh catalyst - lower than 0,5 kg/t of

feed

Topchiev Institute of Petroleum Synthesis RAS

Production of the low molecular weight olefins or high-octane gasoline from natural gas via dimethyl ether 

Syngas

Gasoline,Olefins

Methanol DME

Natural gas

DME

Perspective routeTraditional route

Stage of “syngas to DME” is more effective and cheaper that stage “syngas to methanol”

Stage “DME to hydrocarbons” is simpler and more effective than stage “methanol to hydrocarbons”

Process schemes of conversion of natural gas to olefins

Catalyst — NiO+Co3O4/Al2O3

CH4 + MeOx CO + H2

МеМеМеOxМеOx

O2 +MeO2 +Me

Air

Nitrogen

CO + H2

CH4

Zone of reaction

(reduction of catalyst)

Zone of reaction

(reduction of catalyst)

Zone of regeneration

(oxidation of catalyst)

Zone of regeneration

(oxidation of catalyst)

Pilot unit scheme with

circulating fluidized

catalyst bed

Pilot plant: DME and gasoline production

New technology and catalyst of oxidizing conversion of methane to syngas have been developed

New technology and catalyst of direct DME production from syngas have been developed

New technology and catalyst of gasoline production from DME have been developed

New technology and catalyst of lower olefins production from DME have been developed

Octane number (r.m.) 92 - 93

Aromatics(vol. %) < 20

Aliphatics (vol. %) > 80

Topchiev Institute of Petroleum Synthesis RAS

Functional Materials

2.7. Nanostructured membrane materials membrane materials, membrane reactors and membrane catalysis for the

production of valuable chemical products;-nanostructured membranes with improved transport properties and

devices for gases and liquids purification and separation.

2.8. Biomimetic materials and materials for medicine bioresorbable materials for bone and dental implants; biodegradable and transdermal systems with controlled drugs release; systems with high adhesion to various substrates, including biological, for

use as protective coatings, packaging, etc.

Membranes from anodic aluminum oxide

MSU, Department of material science

Laboratory membrane catalyst setting for ethane oxidative dehydrogenation to ethylene (ODE) allows to carry out the process at ratios of ethane and oxygen, unacceptable in conventional reactors

Scheme of membrane reactorODE was carried out at 320-460 C in a flow reactor.

Increase in ethane conversion up to 70% with 95% selectivity.

Reactants conversion in membrane reactor

The possibility of membrane reactors use for non-oxidizing methane dimerization under the UV irradiation to yield compounds C2 and more

• Excitation of CH4 molecules by ultraviolet radiation allows to activate methane at 500-600 K. The use of membrane reactor allows to shift the thermodynamic balance dew to the removal of hydrogen from the reaction zone.

Topchiev Institute of Petroleum Synthesis RAS

Zelinskii Institute of Organic Chemistry RAS

Topchiev Institute of Petroleum Synthesis RAS

Catalytic membrane contactor/reactor for O2 remove from water

Principle

Catalytic membranes synthesized

Pd

Single-stage process

Deposition of Pd onto hydrophobic polymeric porous membranes

Water Water

GasGas Liquid-Cell contactor

0

0,2

0,4

0,6

0,8

1

1,2

1,4

1,6

1,8

2

2,2

2,4

150 200 250 300 350 400 450 500 550 600 650 700 750 800 850 900

time, min

Con

cent

ratio

n D

O, p

pb0

1

2

3

4

5

6

7

8

9

0 10 20 30 40 50 60 70 80 90 100 110 120 130 140 150 160

time, min

Co

ncen

trati

on

DO

, p

pm

1 ppb

Topchiev Institute of Petroleum Synthesis RAS

Hydrodechlorination of trichlorethylene (TCE) at room temperature

porous membranes, TNO, Holst center

SEM image of the cross-cleaved HA coating on the Ti surface (a) and AFM-iso-ping cross-cleavage of the covering thickness of 3.0 mm HA (b)

1 - nanocrystalline HA coating on titanium (1mkm) after TiO2 - nanocrystalline HA coating on silicon (1mkm)3 - nanocrystalline HA coating on titanium (1mkm)4 - nanostructured ceramics5 - amorphous HA coating on titanium (1mkm)6 - nanocrystalline Cu film (1mkm) on Si

TEM image of amorphous HA

Voronezh State University Institute of Metallurgy of RAS

Hydroxylapatite material for implants and its coatings

Polymer adhesives for medical applications

New family of hydrophilic pressure-sensitive adhesives based on interpolymeric complexes:

Adhesion to hydrophilic and wet surfaces; Obtained from non-adhesive materials by simple mixing

Control of dissolution rate is possible; Opportunity for preparation of PSAs with adhesive properties triggerred by external

factors: temperature, pH, humidity.

Other applications: Medical patches; Wound dressings;

Teeth whitening and oral care products

TIPS RAS

Application in transdermal and transmucosal drug delivery systems: Extension of the number of drugs that can be successfully delivered transdermally;

Suitable for delivery of hydrophilic drugs via transdermal route; Excellent for transmucosal delivery due to good adhesion to wet surfaces and wide

range of solubility rates: from rapidly soluble to insoluble in water.

FFP

FFP

LLCT

P

Topchiev Institute of Petroleum Synthesis RAS

Smart pressure-sensitive adhesives

Wound dressings with temperature-assisted painless removal

Phase I: Wound (<39oC)

Wound

Phase II: Wound protection by dressing (<39oC)

Phase III: Healing (<39oC)

Phase IV: Heating of dressing (~40-50°C)

Phase V: Painless dressing removal

Phase VI: Isolation of biomaterials by simple folding

TIPS RASTopchiev Institute of Petroleum Synthesis RAS

Carbohydrates. Novel pharmaagents under development and target diseases

Inflammation: - Blockers of P-, E-, and L-selectins (synthetic compounds)

Cancer: - Blockers of estrogen receptor (natural lignan from Siberian larch; pre-clinical);

- Inhibitors of metastasis development (synthetic compounds)

- Antiangiogenic agents (synthetic compounds)

- Sensitizer for photodynamic therapy (synthetic compound, EMA approved)

- Glycoconjugate oncovaccines (synthetic compound)

Neural diseases: - Blockers of auto-antibodies which cause neuropathies (synthetic carbohydrate HNK-1 antigens and ganglioside ligands and their mimetics)

- Stimulators of neurith outgrowth (synthetic compounds)

Infection diseases: - Oligodentate blockers of bacterial toxins (synthetic compounds)

- Glycoconjugate bacterial and fungal vaccines (synthetic compounds)

Zelinskii Institute of Organic Chemistry RAS

Drugs and materials with biological activity