Metals Production in The Future

Transcription

1 Laboratory of Chemical Reactor Engineering Metals Production in The Future Opportunities for Spinning Disc Technology John van der Schaaf

2 Laboratory of Chemical Reactor Engineering Chemicals Production in The Future Opportunities for Spinning Disc Technology John van der Schaaf

3 Chemicals Production in the Future: Energy, Raw Materials, Capital & Risk 50 TW Wind Turbines 5 TW Highly variable supply Distributed production Storage/transport inefficient Use for chemicals production Highly variable production rate

4 Chemicals Production in the Future: Energy, Raw Materials, Capital & Risk 0.5 MW Highly variable resources Biomass, recycle, waste Distributed production Safe, robust, efficient, versatile equipment + processes

5 Chemicals Production in the Future: Energy, Raw Materials, Capital & Risk Low CAPEX High ROI Multipurpose, Scalable Robust, Safe Millions vs. Billions

6 Multiphase Systems: Bottlenecks Reaction rate kinetically limited mass transfer limited Gas Liquid Solid Catalyst concentration/activity C g a gl C L a s δ r A 1 H H H = C k a k a k a ηk Lδa g g gl l gl s s r t s 1 Gas Liquid Solid rr AA HH RR VV RR = UUUU TT llll

7 Rotor Stator Spinning Disc Reactor Von Karman Liquid flow only

8 Rotor Stator Spinning Disc Reactor Von Karman 35 rpm; slowed down factor rpm; slowed down factor 120

9 Rotor Stator Spinning Disc Reactor disc rotational speed: 1500 rpm; gas flow rate: 500 ml/min 1 gas inlet movies slowed down factor gas inlets

10 Mass Transfer v r v θ Gas bubbles detach from gas inlet due to shear: Increase in gas-liquid interfacial area a GL High rate of renewal of liquid at bubble interface: Increase in mass transfer coefficient k L

11 Mass Transfer Bubble column: ka < 0.15 m m s L GL L R Bubble column: ka L ε G GL 0.5 m m s L G

12 Gas-Liquid Mass Transfer Van Eeten et al., A theoretical study on gas-liquid mass transfer in the rotor stator spinning disc reactor, CES

13 Multiple Spinning Discs Reactor Diameter disc 13.2 cm Maximum disc speed 4000 rpm Disc spacing mm Cooled or heated discs Discs coated with catalyst Co- and countercurrent operation

14 Spinning Disc Technology Technical characteristics: High mass transfer (GL ~ 10 1/s, LL ~ 300 1/s, LS ~ /s) High heat transfer (U. A ~ 40 MW/m 3 /K) Short micro mixing times (t m ~ 0.1 ms) Counter-current flow ( kg/hr) Plug flow (~ 4 tons/hr) Low volume ( V R ~ 1 L) Application areas: Extreme fast and exothermic reactions (nitrification) Multiphase reactions (sulfonation, halogenation) Extraction (LL, LS) Distillation (RPB), Absorption Crystallization Electrochemistry, Photochemistry

15 Intensification Chlor-alkali production Dot on the horizon State-of-the-art operation (now) 15 kton/yr High pressure operation (~10 bar) High current density operation High temperature operation (~150 ºC)

16 Vision Back-of-a-truck production plant Dot on the (10 horizon kton/yr~ 1 m 3 ) Transported to clients Plug n Produce Remote controlled Transport NaCl from clients or... recycle salt stream

17 Intensification Chlor-alkali production Cl 2 (l) + H 2 O(l) Cl 2 7,2H 2 O Cl 2 (l) + Hydrate(s) Cl 2 (g) + H 2 O(l) Cl 2 (g) + Hydrate(s) 0.35 m 3 /s 1 m 3 /s 2 % 25 % H 2 SO 4 Source: A. T. Bozzo et al., 1975

18 Intensification Chlor-alkali production

19 Intensification Chlor-alkali production 0.03 ka/m 2, 2.33 V 0.12 ka/m 2, 3.03 V 0.21 ka/m 2, 3.59 V 0.30 ka/m 2, 4.32 V 0.39 ka/m 2, 4.60 V 1.40 ka/m 2, 9.92 V

20 Intensification Chlor-alkali production 300 rpm 1000 rpm Centrifugal force removes bubbles from electrode Turbulence increases mass transfer

21 Intensification Chlor-alkali production Sherwood (-) x Grunow Soo&Princeton Disc Mesh Mesh (fit) k LS a LS Disc(Ir) Mesh (Ir) Reynolds (-) x Sh=2.2Re Sc Reynolds (-) x10 5 Disc: a = 477 m / m 2 3 LS e. a. R Mesh: a = 1322 m / m 2 3 LS e. a. R

22 Intensification Chlor-alkali production Paola Granados-Mendoza Shohreh Moshtarikhah

23 Intensification Chlor-alkali production Voltage [V] current density [ka.m -2 ] voltage=4 V rpm Voltage [V] 1 Electrocell Spinning Disc Electrolyser current density [ka.m -2 ] 3.14 ka.m rpm

24 Intensification Chlor-alkali production Cl 2 (l) + H 2 O(l) Cl 2 7,2H 2 O Cl 2 (l) + Hydrate(s) 300 ppm m 3 /s 0.05m 3 /s 1 % Cl 2 (g) + H 2 O(l) Cl 2 (g) + Hydrate(s) 0.35m 3 /s 1m 3 /s 2 % 25 % H 2 SO 4 Source: A. T. Bozzo et al., 1975

25 Intensification Chlor-alkali production Dot on the horizon: Electrolysis: 8 m 2, 100 ka/m 2 16 discs, 0.8 m ID, 0.08 m 3 Chlorine drying: <0.5 m 3 Evaporation: ~ 1 m 3 State-of-the-art operation (now) 15 kton/yr High pressure operation (~10 bar) High current density operation High temperature operation (~150 ºC)

26 Spinning Disc Zinc Production Molten zinc metal can be easily transformed in small particles (µm range)

27 Zinc hydrogen production 1) Zinc + Concentrated sulfuric acid (10 mol/l) Zn (s) + 2 H + (aq) Zn 2+ (aq) + H 2(g) (ambient, 0.9 mol H2 /L, 0.36 mol H2 /kg) 2) Addition of catalytic amount of copper + Hot water Zn (s) + 2 H 2 O (l) Zn(OH) 2(s) + H 2(g) (~100 o C, 28 mol H2 /L, 21 mol H2 /kg) 3) Molten zinc + steam Zn (l) + H 2 O (g) ZnO (s) + H 2(g) (~450 o C, 55 mol H2 /L, 34 mol H2 /kg) Exothermic!

28 Iron Fuel: gas phase oxidation/reduction Cyclic operation packed bed Energy production from heat of oxidation 2 Fe + 3/2 O 2... Fe 2 O 3 + ΔH R = -823 kj/mol Fe Fe 2 O H 2... Fe + 3 H 2 O + ΔH R = +196 kj/mol Fe T>570 o C 1) Oxygen from air: high T leads to NO x 2) Oxygen and hydrogen from water electrolysis (recycle water) 3) Direct electrochemical reduction after dissolution Fe 2 O 3 in sulfuric acid Fe 2+ (aq) + 2 e- Fe (s) Solid iron poorly accessible for oxygen

29 Dendrite formation One-dimensional ferromagnetic dendritic iron wire array growth by facile electrochemical deposition, Nanoscale 4 (2012) , DOI: /C2NR11780KRi Qiu, et al.,

30 Use of oxygen from electrolysis 13 1 kw 14 MJ/kg, 58 MJ/L kw

31 Ragone Chart 10 7 Fe 10 6 Fe Fe k g a g =30 1/s C O2 = 13 mol/m 3 ~40 mol Fe /m R3 /s ~32 MW

32 A(S) Current & Future Work: Chemical Production Process A(S), C(S), D(S) D(s) Reactor Extractor E Crystallizer B(g) C(E), D(E) E Evaporation C(E), D(E) D(E) Crystallizer C(s) A(S) + B(g) ----> C(S) C(S) + B(g) ----> D(S)

33 Current & Future Work: Chemical Production Process

34 Current & Future Work: Chemical Production Process

35 Current & Future Work: Chemical Production Process