ADVANCED CATALYTIC STUDIES FOR POWER ENGINEERING AND ENVIRONMENTAL PROTECTION

Transcription

1 ADVANCED CATALYTIC STUDIES FOR POWER ENGINEERING AND ENVIRONMENTAL PROTECTION Z.R. Ismagilov Boreskov Institute of Catalysis

2 CONTENTS OF THE LECTURE Introduction Catalytic combustion Catalytic heaters Catalytic boilers Catalytic fluidized bed combustion Catalytic two-stage combustion Catalytic combustion for Gas Turbines Fuel Cells

3 CATALYSIS FOR POWER ENGINEERING AND ENVIRONMENT Exhaust gas purification, liquid and solid waste treatment Power engineering Transport Industry Agriculture Flameless catalytic fuel combustion Kinetics and mechanism New catalyst synthesis Methods of catalytic combustion Creation of new environmentally safe productions Industrial technology Creation of new environmentally safe products

4 KEY ROLE OF CATALYSIS Fuel production - 100% Fuel combustion - >0,1% Fuel cells - 100% Exhaust abatement - 80%

5 CATALYSIS FOR POWER ENGENEERING Increase combustion efficiency Improve environmental protection

6 FUEL COMBUSTION Traditional Combustion (Chain Mechanism) flame RH + O 2 CO 2 + H 2 O + Q 1 t > 1200 oc CO + Benz[ α ]pyren N 2 + O 2 NO, NO 2 thermal NO x RNH + O 2 NO x +... fuel NO x Heterogeneous Catalytic Oxidation (Low Temperature Flameless Combustion) RH + O 2 catalyst t= oc CO 2 + H 2 O + Q 2 N 2 + O 2 NOx RNH + O 2 RNH + O 2 k1 k2 N2 + CO 2 + H 2O NOx + CO2 + H 2O

7 Dependence of NO x concentration on temperature at combustion of fuel containing 1 wt.% of bound nitrogen: Flame combustion ( - fuel NO x, - thermal NO x ) Catalytic combustion ( - fuel NO x, - thermal NO x ) equilibrium NO x concentration

8 Advantageous Fields of Catalytic Combustion Development Greenhouse effect - energy saving industrial technologies based on catalytic combustion, to diminish CO 2 formation. Environmentally safe transport - new generation of engines on the principles of catalytic fuel combustion; - catalytic purification of automotive exhaust: combustion of hydrocarbons, CO, aldehydes, soot particles, etc. Environmental problems of energy production - catalytic combustion in gas turbines and boilers; - catalytic fluidized bed combustion; - two-stage catalytic combustion; - catalytic space heaters, household appliances. VOC Control Environmental impact of oil and gas mining, transportation

9 MAIN APPLICATIONS OF CATALYTIC FUEL COMBUSTION Catalytic gas heaters Boilers Two-stage combustion Gas turbines Fuel cells

10 TYPES OF CATALYTIC BURNERS 1. Fluidized bed (CHG) 2. Fixed bed 3. Ceramic monolith honeycomb catalysts 4. Two-stage combustion 5. Foam material catalysts (diameter mm)

11 CATALYTIC GAS HEATERS Catalyst support Fiber materials Ceramic monoliths Active component Low ignition temperature High thermal stability

12 Catalytic Gas Heaters «Termokat»

13 CATALYTIC BURNER Mn containing catalyst on highly porous foam material, diameter 300 mm

14 CATALYTIC COMBUSTION GAS BOILER Distinctive features: Full combustion of natural gas; No nitrogen oxides in the exhaust; Carbon oxide concentration is below 0,01 vol. %. Technical characteristics: Rated heat power, kw Efficiency, % Water temperature at the output, C Flue gas temperature, C, not less. 110 Natural gas consumption at 1270 Pa pressure, m 3 /hour 1.6 Dimensions, mm x440x440 Mass, kg... 90

15 Fluidized Bed Catalytic Combustion Schematic of Catalytic Heat Generator

16 Scheme of Phase Transitions in Supported Copper-Chromium Catalyst CuCr 2 O 7 nh 2 O + γ-al 2 O 3 CuCr 2 O 7 nh 2 O + α-al 2 O 3 CuCr 2 O 7 nh 2 O + (γ+χ)-al 2 O 3 970K γ-al 2 O 3 <CuCr 2 O 4 (trace) - X-ray CrO 3-2 wt.%,cuo - 1 wt.% CuCr 2-x Al x O 4 CuCr 2 O 4, Cu 2 Cr 2 O 4 (trace) - IR Cr(VI) - ESDR 1170K δ-al 2 O 3,CuCr 2-x Al x O 4 - X-ray CuCr 2-x Al x O 4 Cu 2 Cr 2-x Al x O 4 - IR Cr(VI) - ESDR 1270K α- Cr 2-x Al x O 3, θ-al 2 O 3 α- Al 2-x Cr x O 3 - X-ray CuCr 2-x Al x O 4 - IR α-cr 2 O 3 / a-al 2 O 3 - ESDR 1370K CuCr 2-x Al x O 4, Cu 2 Cr 2-x Al x O 4 α-cr 2-x Al x O 3,a-Al 2-x Cr x O 3 -X-ray Cu 2 Cr 2 O 4,a-Al 2 O 3 -X-ray,ESDR α- Cr 2-x Al x O 3 CrO wt.% CuO - 1wt.% - ESDR CuCr 2-x Al x O 4 α-al 2 O 3 - X-ray CuCr 2-x Al x O 4, α- Cr 2-x Al x O 3 Cu 2 Cr 2-x Al x O 4 - X-ray α Al 2-x Cr x O 3 CuCr 2-x Al x O 4, Cu 2 Cr 2-x Al x O 4 γ-al 2 O 3, d-al 2 O 3 - IR α- Al 2-x Cr x O 3 After catalytic 970K 1270K 1470K combustion Cu 2 Cr 2 O 4, γ-al 2 O 3 χ-al 2 O 3 - X-ray CuCr 2-x Al x O 4 θ-al 2 O 3,α-Al 2 O 3 - X-ray α-al 2 O 3,CuCr 2-x Al x O 4 Cu 2 Cr 2-x Al x O 4 - X-ray 970K 1170K 1370K

17 Activity Catalysts for total oxidation Oxides of transition metals Metals Pt-group Stability Spinel Mineralization of support by Me 3+ MeCo 2 O 4 > MeCr 2 O 4 > MeFe 2 O 4 Support Al 2 O 3 Mineralization of support by Me 2+ Chromates Co, Zn, Ni, Mg, Fe, Mn, Cu Mechanical strength Mechanical strength Mg > Ni, Zn Technology: impregnation of sperical alumina MgCr 2 O 4 /γ-al 2 O 3 support heat treatment, calcination.

18 Catalytic Destruction of Mixed Organic Radioactive Wastes complete destruction of hazardous organic components without secondary emissions compacting, more than fold reduction of volume of radioactive waste for further processing by existing technologies, vitrification

19 PROTOTYPE DEMONSTRATION PLANT FOR MIXED ORGANIC WASTE TREATMENT AT THE PLANT OF CHEMICAL CONCENTRATES, NOVOSIBIRSK Catalytic reactor

20 Catalytic fluidized bed destruction of toxic rocket fuel Objective Environmentally safe and efficient utilization of an extremely toxic and explosive rocket fuel 1,1-dimethylhydrazine: CH 3 N NH 2 CH 3 unsymmetrical dimethylhydrazine, UDMH, technical name - heptyl Method Total catalytic oxidation of UDMH by air in a fluidized bed reactor

21 Schematics of a Pilot Plant for Catalytic Utilization of UDMH

22 Photograph of the Pilot Plant for UDMH Catalytic Fluidized Bed Destruction

23 CATALYTIC AIR HEATER TWO-STAGE COMBUSTION Oxygen / Fuel ratio (α) at first stage 1 Monolith honeycomb catalyst

24 TWO STAGE COMBUSTION Catalytic cartridges

25 Two-stage catalytic heat generators has been successfully used for greenhouse heating at farm Priobskoe near Novosibirsk, Russia during the last three years

26 Catalytic gas turbines is a new approach in environmentally clean power production The use of a catalytic burner in a gas turbine allows: reduction of combustion temperature stabilization of combustion of lean mixtures reduction of NO x, CO and HC emissions

27 Conventional gas turbine Gas turbine with catalytic combustor Catalytica combustion Systems, Inc.

28 Requirements to catalysts for gas turbines high thermal stability ( o C) resistance to thermal shocks high mechanical strength - P=10 atm, velocity 40 m/s pressure drop less than 3%.

29 METAL MONOLITHIC SUPPORT

30 Plasma spray coating of catalyst on metal foil Laminar (a) and turbulent (b) plasma jet outflow.

31 Micrograph of cross section view of Al 2 O 3 plasma sprayed on metal surface

32 Photo of metal samples with plasma sprayed Al 2 O 3

33 METAL MONOLITH CATALYTIC BURNER

34 Xonon Catalytic Combustion System installed on Kawasaki M1A-13A

35 Catalyst application in fuel cell systems: development focus

36 Main areas of catalysis application for fuel cell technology 1. Hydrogen production from natural gas and other fuels 2. Catalysis of electrochemical reactions in fuel cell electrodes

37 Methods of syn-gas production from methane 1. Steam methane reforming CH 4 + H 2 O = CO + 3 H kj/mole 2. Dry methane reforming CH 4 + CO 2 = 2 CO + 2 H kj/mole 3. Catalytic partial oxidation CH 4 + 1/2 O 2 = CO + 2 H kj/mole

38 Schematic diagram of the process

39 TYPES OF CATALYTIC BURNERS 1. Fluidized bed (CHG) 2. Fixed bed 3. Ceramic monolith honeycomb catalysts 4. Two stage combustion 5. Foam material catalysts (diameter mm)

40 Synthesis of catalysts for combustion of HC fuels. Systematic variation of synthesis conditions Catalyst types Pd containing catalysts based on γ-al 2 O 3 Mn-Al-O catalysts containing MnO x, MnAl 2 O 4, MnLaAl 11 O 19 Pd based catalysts containing MnO x, MnAl 2 O 4, MnLaAl 11 O 19 Pd wt.% Variable synthesis conditions MnO wt.% MgO wt.% La 2 O wt.% Calcination at 1200 о С

41 Synergetic effect of Pd and oxide manganese compounds: MnO x, MnAl 2 O 4, MnLaAl 11 O CH 4 conversion, % T 50% =460 o C T 50% =395 o C T 50% =350 o C T 50% =530 o C - MnO x /Al 2 O 3 - Pd/Al 2 O 3 - Pd/MnO x /Al 2 O 3 - (Mn,Mg)LaAl 11 O 19 - Pd/HA precursor-(mn,mg)laal 11 O 19 - Pd/HA-(Mn,Mg)LaAl 11 O T 50% =430 o C T 50% =415 o C Temperature, o C Pd/MnO x /γ-al 2 O 3 (Т 50% =415 о С) Pd/γ-Al 2 O 3 (Т 50% =430 о С) < Pd/HA-(Mg,Mn)LaAl 11 O 19 (Т 50% =395 о С) < Pd/HA precursor-(mn,mg)laal 11 O 19 (Т 50% =350 о С)

42 Catalytic burners for reformers of fuel cell energy installations Two types of catalysts